Modified carbide and oxycarbide containing catalysts and methods of making and using thereof

ABSTRACT

Compositions including modified carbide-containing nanorods and/or modified oxycarbide-containing nanorods and/or modified carbon nanotubes bearing carbides and oxycarbides and methods of making the same are provided. Rigid porous structures including modified oxycarbide-containing nanorods and/or modified carbide containing nanorods and/or modified carbon nanotubes bearing modified carbides and oxycarbides and methods of making the same are also provided. The compositions and rigid porous structures of the invention can be used either as catalyst and/or catalyst supports in fluid phase catalytic chemical reactions. Processes for making supported catalyst for selected fluid phase catalytic reactions are also provided.

RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. applicationSer. No. 09/615,350 filed Jul. 12, 2000 which is a continuation-in-partof U.S. application Ser. No. 09/481,184 filed Jan. 12, 2000 based onU.S. Provisional Patent Application No. 60/115,735 filed Jan. 12, 1999,which applications are hereby incorporated by reference in theirentirety.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The invention relates to modified, e.g., acidified, compositionsof carbide-containing and oxycarbide-containing nanorods, carbonnanotubes including carbide and/or oxycarbide compounds, rigid porousstructures including these compositions, and methods of making and usingthe same. More specifically, the invention relates to modified rigidthree dimensional structures comprising carbide and/oroxycarbide-containing nanorods or carbon nanotubes bearing carbides andoxycarbides, having high surface areas and porosities, low bulkdensities, substantially no micropores and increased crush strengths.The invention also relates to using the modified compositions and therigid porous structures including these compositions as catalysts andcatalyst supports, in heterogeneous catalytic reactions frequentlyencountered in petrochemical and refining processes.

[0004] 2. Description of the Related Art

[0005] Heterogeneous catalytic reactions are widely used in chemicalprocesses in the petroleum, petrochemical and chemical industries. Suchreactions are commonly performed with the reactant(s) and product(s) inthe fluid phase and the catalyst in the solid phase. In heterogeneouscatalytic reactions, the reaction occurs at the interface between thephases, i.e., the interface between the fluid phase of the reactant(s)and product(s) and the solid phase of the supported catalyst. Hence, theproperties of the surface of a heterogeneous supported catalyst areimportant factors in the effective use of the catalyst. Specifically,the surface area of the active catalyst, as supported, and theaccessibility of that surface area to reactant adsorption and productdesorption are important. These factors affect the activity of thecatalyst, i.e., the rate of conversion of reactants to products. Thechemical purity of the catalyst and the catalyst support have animportant effect on the selectivity of the catalyst, i.e., the degree towhich the catalyst produces one product from among several products andthe life of the catalyst.

[0006] Generally catalytic activity is proportional to catalyst surfacearea. Therefore, a high specific area is desirable. However, the surfacearea should be accessible to reactants and products as well as to heatflow. The chemisorption of a reactant by a catalyst surface is precededby the diffusion of that reactant through the internal structure of thecatalyst.

[0007] Since the active catalyst compounds are often supported on theinternal structure of a support, the accessibility of the internalstructure of a support material to reactant(s), product(s) and heat flowis important. Accessibility is measured by porosity and pore sizedistribution. Activated carbons and charcoals used as catalyst supportsmay have surface areas of about a thousand square meters per gram andporosities of less than 1 ml/gm. However, much of this surface area andporosity, as much as 50%, and often more, is associated with micropores,i.e., pores with pore diameters of 2 nm or less. These pores can beinaccessible because of diffusion limitations. They are easily pluggedand thereby deactivated. Thus, high porosity material where the poresare mainly in the mesopore region, i.e., greater than 2 nm or macroporeregion, i.e., greater than 50 nm, ranges are most desirable.

[0008] It is also important that self-supported catalysts and supportedcatalysts not fracture or attrit during use because such fragments maybecome entrained in the reaction stream and must then be separated fromthe reaction mixture. The cost of replacing attritted catalyst, the costof separating it from the reaction mixture and the risk of contaminatingthe product are all burdens upon the process. In slurry phase, e.g.where the solid supported catalyst is filtered from the process streamand recycled to the reaction zone, the fines may plug the filters anddisrupt the process. It is also important that a catalyst, at the veryleast, minimize its contribution to the chemical contamination ofreactant(s) and product(s). In the case of a catalyst support, this iseven more important since the support is a potential source ofcontamination both to the catalyst it supports and to the chemicalprocess. Further, some catalysts are particularly sensitive tocontamination that can either promote unwanted competing reactions,i.e., affect its selectivity, or render the catalyst ineffective, i.e.,“poison” it. For example, charcoal and commercial graphites or carbonsmade from petroleum residues usually contain trace amounts of sulfur ornitrogen as well as metals common to biological systems and may beundesirable for that reason.

[0009] Traditionally, noble metal catalysts, such as platinum andruthenium, have been used as catalysts in heterogeneous reactions.Because of the expense associated with the noble metal catalysts, manyworkers have sought to achieve a “poor man's platinum” through the useof metal carbides. To control the catalytic activity of metal carbides,2 important factors need to be realized. First, the carbide particlesneed to have nanoscale dimensions in order to possess enough surfacearea. Second, the catalyst may need to undergo surface modifications toenhance the catalyst's ability to obtain special selectivity.

[0010] Since the 1970s carbon nanofibers or nanotubes have beenidentified as materials of interest for use as catalysts and catalystsupports. Carbon nanotubes exist in a variety of forms and have beenprepared through the catalytic decomposition of variouscarbon-containing gases at metal surfaces. Nanofibers such as fibrils,bucky tubes and nanotubes are distinguishable from continuous carbonfibers commercially available as reinforcement materials. In contrast tonanofibers, which have, desirably large, but unavoidably finite aspectratios, continuous carbon fibers have aspect ratios (L/D) of at least10⁴ and often 10⁶ or more. The diameter of continuous fibers is also farlarger than that of nanofibers, being always greater than 1 μm andtypically 5 μm to 7 μm.

[0011] U.S. Pat. No. 5,576,466 to Ledoux et al. discloses a process forisomerizing straight chain hydrocarbons having at least 7 carbon atomsusing catalysts which include molybdenum compounds whose active surfaceconsists of molybdenum carbide which is partially oxidized to form oneor more oxycarbides. Ledoux et al. disclose several ways of obtaining anoxycarbide phase on molybdenum carbide. These methods require theformation of molybdenum carbides by reacting gaseous compounds ofmolybdenum metal with charcoal at temperatures between 900° C. and 1400°C. These are energy intensive processes. Moreover, the resultingmolybdenum carbides have many drawbacks similar to catalysts preparedwith charcoal. For example, much of the surface area and porosity of thecatalysts is associated with micropores and as such these catalysts areeasily plugged and thereby deactivated.

[0012] While activated charcoals and other materials have been used ascatalysts and catalyst supports, none have heretofore had all of therequisite qualities of high surface area, porosity, pore sizedistribution, resistance to attrition and purity for the conduct of avariety of selected petrochemical and refining processes. Although manyof these materials have high surface area, much of the surface area isin the form of inaccessible micropores.

[0013] It would therefore be desirable to provide a family ofcarbide-containing and oxycarbide containing catalysts that have highlyaccessible surface area, high porosity, and attrition resistance, andwhich are substantially micropore free, highly active, highly selectiveand are capable of extended use with no significant deactivation.

OBJECTS OF THE INVENTION

[0014] It is an object of the present invention to provide a method ofmodifying the surface of a carbide-containing or oxycarbide-containingcatalyst and/or a carbide-containing or oxycarbide-containing catalystsupport to improve its properties.

[0015] It is a related object of the present invention to provide amethod of modifying the surface of a carbide-containing oroxycarbide-containing catalyst and/or a carbide-containing oroxycarbide-containing catalyst support to improve its selectivity.

[0016] It is a further object of the present invention to provide amethod of modifying the surface of a carbide-containing oroxycarbide-containing catalyst and/or a carbide-containing oroxycarbide-containing catalyst support to improve its selectivity inhydrocarbon skeletal isomerizations.

[0017] It is another object of the present invention to provide suchcatalyst compositions and/or catalyst supports having modified surfaces.

[0018] It is yet a further object of the present invention to providesuch catalyst compositions and/or catalyst supports having surfacesmodified to improve reaction selectivity.

[0019] It is yet another and further object of the present invention toprovide such catalyst compositions and/or a catalyst supports havingsurfaces modified to improve reaction selectivity in hydrocarbonskeletal isomerizations.

[0020] It is another object of the present invention to provide acomposition of a catalyst and/or a catalyst support that has had itssurface modified.

[0021] It is a further object of the present invention to provide acomposition of a catalyst and/or a catalyst support that has had itssurface modified to improve its selectivity.

[0022] The foregoing and other objects and advantages of the inventionwill be set forth in or will be apparent from the following descriptionand drawings.

SUMMARY OF THE INVENTION

[0023] The present invention is in compositions comprising carbidenanorods which contain oxycarbides.. Another composition of the presentinvention comprises carbide-containing nanorods which also containoxycarbides. Another composition comprises carbon nanotubes which bearacidified carbides and/or oxycarbides on the surfaces thereof. In onecomposition the carbides retain the structure of the original aggregatesof carbon nanotubes. Compositions are also provided which includecarbide-containing nanorods where the morphology of the aggregates ofcarbon nanotubes is not retained. The invention also provides acomposition of carbides supported on carbon nanotubes where a portion ofthe carbon nanotubes have been converted to carbide-containing nanorodsand/or carbides.

[0024] The present invention also provides rigid porous structuresincluding acidified oxycarbide nanorods and/or carbide-containingnanorods and/or carbon nanotubes bearing carbides and oxycarbides.Depending on the morphology of the carbon nanotubes used as a source ofcarbon, the rigid porous structures can have a uniform or non-uniformpore distribution. Extrudates of acidified oxycarbide nanorods and/orcarbide-containing nanorods and/or carbon nanotubes bearing oxycarbidesand/or carbides are also provided. The extrudates of the presentinvention are glued together to form a rigid porous structure.

[0025] The compositions and rigid porous structures of the invention canbe used either as catalysts and/or catalyst supports in fluid phasecatalytic chemical reactions.

[0026] The present invention also provides methods of makingoxycarbide-containing nanorods, carbide-containing nanorods bearingoxycarbides and carbon-nanotubes bearing carbides and oxycarbides.Methods of making rigid porous structures are also provided. Rigidporous structures of carbide-nanorods can be formed by treating rigidporous structures of carbon nanotubes with a Q-containing compound,i.e., a compound containing a transition metal, a rare earth or anactinide. Depending upon conditions the conversion of the carbonnanotubes to carbide-containing nanorods can be complete or partial. Therigid porous structure of carbide nanorods and/or carbon nanotubes canbe further treated with an oxidizing agent to form oxycarbide nanorodsand/or oxycarbides. The rigid porous structures of the invention canalso be prepared from loose nanorods or aggregates of carbide-containingnanorods and/or oxycarbide-containing nanorods by initially forming asuspension in a medium, separating the suspension from the medium, andpyrolyzing the suspension to form rigid porous structures. The presentinvention also provides a process for making supported catalysts forselected fluid phase reactions.

[0027] Other improvements which the present invention provides over theprior art will be identified as a result of the following descriptionwhich sets forth the preferred embodiments of the present invention. Thedescription is not in any way intended to limit the scope of the presentinvention, but rather only to provide a working example of the presentpreferred embodiments. The scope of the present invention will bepointed out in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings, which are incorporated in andconstitute a part of the specification, illustrate an exemplaryembodiment of the present invention.

[0029]FIG. 1A is an XRD graph of sample 12 as set forth in Table 1. Areference XRD pattern of hexagonal Mo₂C is shown immediately below.

[0030]FIGS. 1B and 1C are SEM micrographs of sample 12 as set forth inTable 1.

[0031]FIG. 2A is an XRD graph of sample 12 as set forth in Table 1. Areference XRD pattern of hexagonal Mo₂C is also shown immediately below.

[0032]FIG. 2B is an HRTEM micrograph of sample 12 as set forth in Table1.

[0033]FIG. 3A is an XRD graph of sample 10 as set forth in Table 1.Reference XRD patterns of hexagonal Mo₂C, cubic Mo₂C and graphite areshown immediately below.

[0034]FIG. 3B is an HRTEM micrograph of sample 10 as shown in Table C.

[0035]FIG. 4 is a thermogravimetric analysis of sample 12 as set forthin Table 1.

[0036]FIG. 5A is an SEM micrograph of SiC extrudates.

[0037]FIG. 5B is an SEM micrograph illustrating micropores among theaggregates of the extrudates shown in FIG. 5A.

[0038]FIG. 5C is an SEM micrograph illustrating micropores in thenetworks of the intertwined SiC nanorods present in the extrudates shownin FIG. 5A.

DETAILED DESCRIPTION OF THE INVENTION

[0039] Patents, patent applications, and patent publications arereferred to herein are incorporated by reference in their entirety.

[0040] Definitions

[0041] “Acidifying compound” means any compound capable of imparting anacidic characteristic to a catalyst and/or a catalyst support.Acidifying compound includes any compound that is capable of acceptingelectrons. “Accessible surface area” refers to that surface area notattributed to micropores.

[0042] “Aggregate” refers to a dense, microscopic particulate structure.More specifically, the term “assemblage” refers to structures havingrelatively or substantially uniform physical properties along at leastone dimensional axis and desirably having relatively or substantiallyuniform physical properties in one or more planes within the assemblage,i.e. they have isotropic physical properties in that plane. Theassemblage may comprise uniformly dispersed individual interconnectednanotubes or a mass of connected aggregates of nanotubes. In otherembodiments, the entire assemblage is relatively or substantiallyisotropic with respect to one or more of its physical properties. Thephysical properties which can be easily measured and by which uniformityor isotropy are determined include resistivity and optical density.

[0043] “Bifunctional catalyst” means a catalyst that contains twodistinct types of catalytic sites in close proximity, for example on thesame support, so that two chemical reactions, for example sequentialchemical reactions, can occur with one adsorption event.

[0044] “Bimodal pore structure” refers to a specific pore structureoccurring when aggregate particles of nanotubes and/or nanorods arebonded together. The resulting structure has a two-tiered architecturecomprising a macro structure of nanotube aggregates having macroporesamong the bundles of nanotube aggregates and a microstructure ofintertwined nanotubes having a pore structure within each individualbundle of aggregate particles.

[0045] “Carbides” refers to compounds of composition QC or Q₂C. The termalso includes crystalline structures characterized by x-ray diffraction(“XRD”) as QC or Q₂C by themselves and/or in combinations with Q or C,e.g., compounds remaining after the synthesis step is substantiallycomplete. Carbides can be detected and characterized by XRD. When, as iscontemplated within the scope of this invention, the carbides areprepared by carburization of metal oxides or by oxidation of elementalcarbon, a certain amount of “non-stoichiometric” carbide may appear, butthe diffraction pattern of the true carbides will still be present.Metal rich non-stoichiometric carbides, such as might be formed from asynthesis wherein the metal is carburized, are missing a few of thecarbons that the metal matrix can accommodate. Carbon richnon-stoichiometric carbides comprise domains of stoichiometric carbidesembedded in the original carbon structure. Once the carbide crystallitesare large enough they can be detected by XRD.

[0046] Carbides also refers to interstitial carbides as morespecifically defined in Structural Inorganic Chemistry, by A. F. Wells,4th Ed., Clarendon Press, Oxford 1975 and in The Chemistry of TransitionMetal Carbides and Nitrides, edited by S. T. Oyama, 1st Ed., a BlackieAcademic & Professional publication 1996. Both books are herebyincorporated by reference in their entirety.

[0047] “Carbide-containing nanorod” refers to a Q-containing nanorodpredominantly having a diameter greater than 2 nm but less than 100 nm,for example greater than 5 nm but less than 50 nm, and having an aspectratio from 5 to 500. When the carbide nanorod has been made byconversion of the carbon of a nanotube to carbide compounds then theconversion has been substantially complete.

[0048] “Fluid phase reaction” refers to any liquid or gas phasecatalytic reactions such as hydrogenation, hydrodesulfurisation,hydrodenitrogenation, hydrodemetallisation, hydrodeoxygenation,protonation, hydrodearomatization, dehydrogenation, hydrogenolysis,isomerization, alkylation, dealkylation, and transalkylation.

[0049] “Graphenic” carbon is a form of carbon whose carbon atoms areeach linked to three other carbon atoms in an essentially planar layerforming hexagonal fused rings. The layers are platelets having only afew rings in their diameter or ribbons having many rings in their lengthbut only a few rings in their width.

[0050] “Graphenic analogue” refers to a structure which is incorporatedin a graphenic surface.

[0051] “Graphitic” carbon consists of layers which are essentiallyparallel to one another and no more than 3.6 angstroms apart.

[0052] “Internal structure” refers to the internal structure of anassemblage including the relative orientation of the fibers, thediversity of and overall average of nanotube orientations, the proximityof the nanotubes to one another, the void space or pores created by theinterstices and spaces between the fibers and size, shape, number andorientation of the flow channels or paths formed by the connection ofthe void spaces and/or pores. According to another embodiment, thestructure may also include characteristics relating to the size, spacingand orientation of aggregate particles that form the assemblage. Theterm “relative orientation” refers to the orientation of an individualnanotube or aggregate with respect to the others (i.e., aligned versusnon-aligned). The “diversity of” and “overall average” of nanotube oraggregate orientations refers to the range of nanotube orientationswithin the structure (alignment and orientation with respect to theexternal surface of the structure).

[0053] “Isotropic” means that all measurements of a physical propertywithin a plane or volume of the structure, independent of the directionof the measurement, are of a constant value. It is understood thatmeasurements of such non-solid compositions must be taken on arepresentative sample of the structure so that the average value of thevoid spaces is taken into account.

[0054] “Macropore” refers to a pore which has a diameter of greater thanor equal to 50 nm.

[0055] “Mesopore” refers to a pore which has a diameter of greater thanor equal to 2 nm but less than 50 nm.

[0056] “Micropore” refers to a pore which has a diameter of less than 2nm.

[0057] “Nanorod” refers to a rod-like structure having a surface and asubstantially solid core with a diameter of at least 1 nm but less than100 nm. The structure has an aspect ratio between 10 and 500 and alength up to 50 μm. The diameter of a nanorod is substantially uniformalong the entire length of the nanorod. A nanorod is solid not hollow.

[0058] “Nanostructure” refers to nanotubes, nanorods, and anycombinations or mixtures of nanotubes and nanorods.

[0059] “Nanotube”, “nanofiber” and “fibril” are used interchangeably.Each refers to an elongated hollow structure having a diameter less than1 μm. The term “nanotube” also includes “bucky tubes” and graphiticnanofibers in which the graphene planes are oriented in herring bonepattern.

[0060] “Nitrogenation” means treatment with any compound containingnitrogen.

[0061] “Nonuniform pore structure” refers to a pore structure occurringwhen individual discrete nanotubes are distributed in a substantiallynonuniform manner with substantially nonuniform spacings betweennanotubes.

[0062] Oxycarbides, unlike carbides, are inherently non-stoichiometric.They are any structure containing oxygen predominantly on the surfaceand derived from a carbide. For example, the oxycarbides of the presentinvention can have the formula:

Q_(n)C_(x−y)O_(y)

[0063] wherein Q is as defined above; n and x are selected to satisfy aknown stoichiometry of a carbide of Q; y is less than x and the ratio[y/(x−y)] is at least 0.02 and less than 0.9 and more preferably isbetween 0.05 and 0.50. Furthermore, the term “oxycarbides” alsoincludes, but is not limited to, products formed by oxidative treatmentsof carbides present in carbon nanotubes used as a source of carbon or inconnection with carbide nanorods as a source of carbides. Oxycarbidescan also include products formed by carburization of metal oxides.Oxycarbides also comprise mixtures of unreacted carbides and oxides,chemisorbed and physisorbed oxygen. More specifically, oxycarbides havea total amount of oxygen sufficient to provide at least 25% of at leastone monolayer of absorbed oxygen as determined by temperature programmeddesorption (TPD) containing on the carbide content of the carbidesource. Oxycarbides also refer to compounds of the same name as definedin The Chemistry of Transition Metal Carbides and Nitrides, edited by S.T. Oyama, a Blackie Academic & Professional Publication. Examples ofoxycarbides include polycrystalline compounds, wherein Q is a metalpreferably in two valent states. Q can be bonded to another metal atomor only to an oxygen or only to a carbon atom. However, Q is not bondedto both oxygen and carbon atoms. The term “carbides” encompasses bothcarbides and oxycarbides.

[0064] “Oxycarbides-containing nanorod” refers to an Q-containingnanorod having the formula Q_(n)C_(x−y)O_(y) as defined above, having anaspect ratio of 5 to 500.

[0065] “Physical property” means an inherent, measurable property of theporous structure, e.g., surface area, resistivity, fluid flowcharacteristics, density, porosity, etc.

[0066] “Phosphorylation” means treatment with any compound containingphosphorus.

[0067] “Pore” traditionally refers to an opening or depression in thesurface of a catalyst or catalyst support. Catalysts and catalystsupports comprising carbon nanotubes lack such traditional pores.Rather, in these materials, the spaces between individual nanotubesbehave as pores, and the equivalent pore size of nanotube aggregates canbe measured by conventional methods (porosimetry) of measuring pore sizeand pore size distribution. By varying the density and structure ofaggregates, the equivalent pore size and pore size distribution can bevaried.

[0068] “Q” represents an element selected from the group consisting oftransition metals (groups IIIB, IVB, VB, VIB, VIIB, and VIII of periods4, 5, and 6 of the Periodic Table), rare earths (lanthanides) andactinides. More preferably, Q is selected from the group consisting ofTi, Ta, Nb, Zr, Hf, Mo, V and W.

[0069] “Q-containing” refers to a compound or composition modifiedreaction with Q as defined above.

[0070] “Relatively” means that 95% of the values of the physicalproperty when measured along an axis of, or within a plane of or withina volume of the structure, as the case may be, will be within plus orminus 20% of a mean value.

[0071] “Substantially” or “predominantly” mean that 95% of the values ofthe physical property when measured along an axis of, or within a planeof or within a volume of the structure, as the case may be, will bewithin plus or minus 10% of a mean value.

[0072] “Surface area” refers to the total surface area of a substancemeasurable by the BET technique as known in the art, a physisorptiontechnique. Nitrogen or helium can be use absorbents to measure thesurface area.

[0073] “Uniform pore structure” refers to a pore structure occurringwhen individual discrete nanotubes or nanofibers form the structure. Inthese cases, the distribution of individual nanotubes in the particlesis substantially uniform with substantially regular spacings between thenanotubes. These spacings (analogous to pores in conventional supports)vary according to the densities of the structures.

[0074] Carbon Nanotubes

[0075] The term nanotubes refers to various carbon tubes or fibershaving very small diameters including fibrils, whiskers, buckytubes,etc. Such structures provide significant surface area when assembledinto a structure because of their size and shape. Moreover, suchnanotubes can be made with high purity and uniformity.

[0076] Preferably, the nanotube used in the present invention have adiameter less than 1 μm, preferably less than about 0.5 μm, and evenmore preferably less than 0.1 μm and most preferably less than 0.05 μm.

[0077] Carbon nanotubes can be made having diameters in the range of 3.5to 70 nm.

[0078] The nanotubes, buckytubes, fibrils and whiskers that are referredto in this application are distinguishable from continuous carbon fiberscommercially available as reinforcement materials. In contrast tonanofibers, which have desirably large, but unavoidably finite aspectratios, continuous carbon fibers have aspect ratios (L/D) of at least10⁴ and often 10⁶ or more. The diameter of continuous fibers is also farlarger than that of fibrils, being always greater than 1 μm andtypically 5 to 7 μm.

[0079] Continuous carbon fibers are made by the pyrolysis of organicprecursor fibers, usually rayon, polyacrylonitrile (“PAN”) and pitch.Thus, they may include heteroatoms within their structure. The graphiticnature of “as made” continuous carbon fibers varies, but they may besubjected to a subsequent graphitization step. Differences in degree ofgraphitization, orientation and crystallinity of graphite planes, ifthey are present, the potential presence of heteroatoms and even theabsolute difference in substrate diameter make experience withcontinuous fibers poor predictors of nanofiber chemistry.

[0080] Carbon nanotubes exist in a variety of forms and have beenprepared through the catalytic decomposition of variouscarbon-containing gases at metal surfaces.

[0081] U.S. Pat. No. 4,663,230 to Tennent hereby incorporated byreference, describes carbon nanotubes that are free of a continuousthermal carbon overcoat and have multiple ordered graphitic outer layersthat are substantially parallel to the nanotube axis. As such they maybe characterized as having their c-axes, the axes which areperpendicular to the tangents of the curved layers of graphite,substantially perpendicular to their cylindrical axes. They generallyhave diameters no greater than 0.1 μm and length to diameter ratios ofat least 5. Desirably they are substantially free of a continuousthermal carbon overcoat, i.e., pyrolytically deposited carbon resultingfrom thermal cracking of the gas feed used to prepare them. Tennentdescribes nanotubes typically 3.5 to 70 nm having an ordered, “as grown”graphitic surface.

[0082] U.S. Pat. No. 5,171,560 to Tennent et al., hereby incorporated byreference, describes carbon nanotubes free of thermal overcoat andhaving graphitic layers substantially parallel to the nanotube axes suchthat the projection of the layers on the nanotube axes extends for adistance of at least two nanotube diameters. Typically, such nanotubesare substantially cylindrical, graphitic nanotubes of substantiallyconstant diameter and comprise cylindrical graphitic sheets whose c-axesare substantially perpendicular to their cylindrical axis. They aresubstantially free of pyrolytically deposited carbon, have a diameterless than 0.1 μm and a length to diameter ratio of greater than 5. Thesefibrils are of primary interest in the invention.

[0083] When the projection of the graphitic layers on the nanotube axisextends for a distance of less than two nanotube diameters, the carbonplanes of the graphitic nanotube, in cross section, take on a herringbone appearance. These are termed fishbone fibrils. U.S. Pat. No.4,855,091 to Geus, hereby incorporated by reference, provides aprocedure for preparation of fishbone fibrils substantially free of apyrolytic overcoat. These carbon nanotubes are also useful in thepractice of the invention. See also, U.S. Pat. No. 5,165,909 to Tennent,hereby incorporated by reference.

[0084] Oxidized nanofibers are used to form rigid porous assemblages.U.S. Pat. No. 5,965,470, hereby incorporated by reference, describesprocesses for oxidizing the surface of carbon nanotubes that includecontacting the nanotubes with an oxidizing agent that includes sulfuricacid (H₂SO₄) and potassium chlorate (KClO₃) under reaction conditions(e.g., time, temperature, and pressure) sufficient to oxidize thesurface of the fibril. The nanotubes oxidized according to the processesof McCarthy, et al. are non-uniformly oxidized, that is, the carbonatoms are substituted with a mixture of carboxyl, aldehyde, ketone,phenolic and other carbonyl groups.

[0085] Nanotubes have also been oxidized nonuniformly by treatment withnitric acid. International Application WO95/07316 discloses theformation of oxidized fibrils containing a mixture of functional groups.Hoogenvaad, M. S., et al. (Metal Catalysts Supported on a Novel CarbonSupport, Presented at Sixth International Conference on Scientific Basisfor the Preparation of Heterogeneous Catalysts, Brussels, Belgium,September 1994) also found it beneficial in the preparation ofnanotube-supported precious metals to first oxidize the nanotube surfacewith nitric acid. Such pretreatment with acid is a standard step in thepreparation of carbon-supported noble metal catalysts, where, given theusual sources of such carbon, it serves as much to clean the surface ofundesirable materials as to functionalize it.

[0086] In published work, McCarthy and Bening (Polymer Preprints ACSDiv. of Polymer Chem. 30 (1)420(1990)) prepared derivatives of oxidizednanotubes in order to demonstrate that the surface comprised a varietyof oxidized groups. The compounds they prepared, phenylhydrazones,haloaromaticesters, thallous salts, etc., were selected because of theiranalytical utility, being, for example, brightly colored, or exhibitingsome other strong and easily identified and differentiated signal.

[0087] Nanotubes may be oxidized using hydrogen peroxide, chlorate,nitric acid and other suitable reagents. See, for example, U.S. patentapplication Ser. No. 09/861,370 filed May 18, 2001 entitled“Modification of Carbon Nanotubes by Oxidation with Peroxygen Compounds”and U.S. patent application Ser. No. 09/358,745, filed Jul. 21, 1999,entitled “Methods of Oxidizing Multiwalled Carbon Nanotubes.”

[0088] The nanotubes within the structure may be further functionalizedas described in U.S. Pat. No. 6,203,814 to Fischer.

[0089] Carbon nanotubes of a morphology similar to the catalyticallygrown fibrils or nanotubes described above have been grown in a hightemperature carbon arc (Iijima, Nature 354 56 1991, hereby incorporatedby reference). It is now generally accepted (Weaver, Science 265 1994,hereby incorporated by reference) that these arc-grown nanofibers havethe same morphology as the earlier catalytically grown fibrils ofTennent. Arc grown carbon nanofibers are also useful in the invention.

[0090] Nanotube Aggregates and Assemblages

[0091] The “unbonded” precursor nanotubes may be in the form of discretenanotubes, aggregates of nanotubes or both.

[0092] As with all nanoparticles, nanotubes aggregate in several stagesor degrees. Catalytically grown nanotubes produced according to U.S.Pat. No. 6,031,711 are formed in aggregates substantially all of whichwill pass through a 700 μm sieve. About 50% by weight of the aggregatespass through a 300 μm sieve. The size of as-made aggregates can, ofcourse, be reduced by various means.

[0093] These aggregates have various morphologies (as determined byscanning electron microscopy) in which they are randomly entangled witheach other to form entangled balls of nanotubes resembling bird nests(“BN”) ; or as aggregates consisting of bundles of straight to slightlybent or kinked carbon nanotubes having substantially the same relativeorientation, and having the appearance of combed yarn (“CY”)—e.g., thelongitudinal axis of each nanotube (despite individual bends or kinks)extends in the same direction as that of the surrounding nanotubes inthe bundles; or, as, aggregates consisting of straight to slightly bentor kinked nanotubes which are loosely entangled with each other to forman “open net” (“ON”) structure. In open net structures the extent ofnanotube entanglement is greater than observed in the combed yarnaggregates (in which the individual nanotubes have substantially thesame relative orientation) but less than that of bird nest. CY and ONaggregates are more readily dispersed than BN.

[0094] When carbon nanotubes are used, the aggregates, when present, aregenerally of the bird's nest, combed yarn or open net morphologies. Themore “entangled” the aggregates are, the more processing will berequired to achieve a suitable composition if a high porosity isdesired. This means that the selection of combed yarn or open netaggregates is most preferable for the majority of applications. However,bird's nest aggregates will generally suffice.

[0095] The morphology of the aggregate is controlled by the choice ofcatalyst support. Spherical supports grow nanotubes in all directionsleading to the formation of bird nest aggregates. Combed yarn and opennest aggregates are prepared using supports having one or more readilycleavable planar surfaces. U.S. Pat. No. 6,143,689 hereby incorporatedby reference, describes nanotubes prepared as aggregates having variousmorphologies.

[0096] Further details regarding the formation of carbon nanotube ornanofiber aggregates may be found in the disclosures of U.S. Pat. Nos.5,165,909; 5,456,897; 5,707,916; 5,877,110; PCT Application No.US89/00322, filed Jan. 28, 1989 (“Carbon Fibrils”) WO 89/07163, and Moyet al., U.S. Pat. No. 5,110,693, U.S. patent application Ser. No.447,501 filed May 23, 1995; U.S. patent application Ser. No. 456,659filed Jun. 2, 1995; PCT Application No. US90/05498, filed Sep. 27, 1990(“Fibril Aggregates and Method of Making Same”) WO 91/05089, and U.S.Pat. No. 5,500,200; U.S. application Ser. No. 08/329,774 by Bening etal., filed Oct. 27, 1984; and U.S. Pat. No. 5,569,635, all of which areassigned to the same assignee as the invention here and of which arehereby incorporated by reference.

[0097] Nanotube mats or assemblages have been prepared by dispersingnanofibers in aqueous or organic media and then filtering the nanofibersto form a mat or assemblage. The mats have also been prepared by forminga gel or paste of nanotubes in a fluid, e.g. an organic solvent such aspropane and then heating the gel or paste to a temperature above thecritical temperature of the medium, removing the supercritical fluid andfinally removing the resultant porous mat or plug from the vessel inwhich the process has been carried out. See, U.S. Pat. No. 5,691,054.

[0098] Extrudates of Carbon Nanotubes

[0099] In a preferred embodiment the carbon rigid porous structurescomprise extrudates of carbon nanotubes. Aggregates of carbon nanotubestreated with a gluing agent or binder are extruded by conventionalextrusion methods into extrudates which are pyrolyzed or carbonized toform rigid carbon structures. If the bundles of carbon nanotubes aresubstantially intact except that they have been splayed (e.g. bysonication) or partially unraveled, the structure provides a bimodalpore structure. The space between bundles ranges from points of contactto about 1 μm. Within bundles, spaces between carbon nanotubes rangefrom 10 to 30 nm. The resulting rigid bimodal porous structure issubstantially free of micropores, has surface areas ranging from about250 m²/gm to about 400 m²/gm and a crush strength of about 20 psi forextrudates of ⅛ inch in diameter. Carbon nanotube extrudates havedensities ranging from about 0.5 gm/cm³ to about 0.7 gm/cm³, which canbe controlled by the density of the extrusion paste. The extrudates haveliquid absorption volumes from about 0.7 cm³/gm.

[0100] Gluing or binding agents are used to form the paste of carbonnanotubes required for extrusion processes. Useful gluing or bindingagents include, without limitation, cellulose, carbohydrates,polyethylene, polystyrene, nylon, polyurethane, polyester, polyamides,poly(dimethylsiloxane), phenolic resins and the like.

[0101] The extrudates obtained as described above can be further treatedwith mild oxidizing agents such as hydrogen peroxide without affectingthe integrity of the rigid porous carbon structures. Subsequently, therigid porous structures can be impregnated with catalytic particles byion exchange, generally a preferred method for deposition of small sizeparticles. Alternatively, the rigid porous carbon structure can also beimpregnated with catalysts by incipient wetness, or physical or chemicaladsorption.

[0102] The rigid, high porosity structures can be formed from regularnanotubes or nanotube aggregates, either with or without surfacemodified nanofibers (i.e., surface oxidized nanotubes). Surface oxidizednanotubes can be cross-linked according to methods described in U.S.Pat. Nos. 6,031,711 and 6,099,965, and then carbonized to from a rigidporous carbon structure having a uniform pore structure, substantiallyfree of micropores.

[0103] Nanorods

[0104] The term nanorods refers to rod-like structures having asubstantially solid core, a surface and a diameter greater than 1nanometer but less than 100 nm. The structure has an aspect ratiobetween 5 and 500 and a length between 2 nm and 50 μm and preferablybetween 100 nm and 20 μm. The disclosed nanorods are substantiallysolid. They are not hollow with one open end, hollow with two open endsor hollow with two sealed ends.

[0105] Carbide Nanorods

[0106] Carbide-containing nanorods can be prepared by using carbonnanotubes as a source of carbon. For example, in WO/00/19121incorporated herein by reference, carbide nanorods were prepared.Q-containing gas was reacted with carbon nanotubes to form, in situ,solid Q-containing carbide nanorods at temperatures substantially lessthan 1700° C. and preferably in the range of about 1000° C. to about1400° C., and more preferably at approximately 1200° C. The Q-containinggases were volatile compounds capable of forming carbides.

[0107] This conversion is called pseudotopotactic because even thoughthe dimensions and crystalline orientations of the starting material andproduct differ, the cylindrical geometry of the starting nanotube isretained in the final nanorod and the nanorods remain separate andpredominately unfused to each other. The diameters of the resultingnanorods were about double that of the starting carbon nanotubes (1nm-100 nm).

[0108] Carbide nanorods have also been prepared by reacting carbonnanotubes with volatile metal or non-metal oxide species at temperaturesbetween 500° C. and 2500° C. wherein the carbon nanotube is believed toact as a template, spatially confining the reaction to the nanotube inaccordance with methods described in PCT/US 96/09675 by C. M. Lieber.See also U.S. patent application Ser. Nos. 09/615,350 and 09/481,184filed Jul. 12, 2000 and Jan. 12, 2000 respectively. Carbide nanorodsformed by methods wherein the carbon nanotube serves as a template arealso useful in the present invention.

[0109] Because of the ease with which they can penetrate fibrilaggregates and rigid porous structures, volatile Q compounds are usuallypreferred. Volatile Q precursors are compounds having a vapor pressureof at least twenty torr at reaction temperature. Reaction with thevolatile Q compound may or may not take place through a non-volatileintermediate.

[0110] Other methods of preparing carbide nanorods include reductivecarburization in which the carbon nanotubes are reacted withQ-containing volatile metal oxides followed by passing a flow of gaseousCH₄H₂ mixture at temperatures between 250° C. and 700° C. In addition toQ-containing metal oxides, volatile Q-containing compounds useful inpreparation of Q-containing carbide nanorods include carbonyls andchlorides such as, for example, Mo(CO)₆, Mo(V) chloride or W(VI)Ochloride.

[0111] In a preferred method of making useful carbide nanorods for thepresent invention, vapors of a volatile Q-containing compound are passedover a bed of extrudates of carbon nanotubes in a quartz tube attemperatures from about 700° C. to about 1000° C. By controlling theconcentration of the Q-containing compound, the crystallization of thecarbides is limited to the space of the nanotubes.

[0112] In all the methods of providing carbide-containing nanorodsdiscussed above, the extent of conversion of the carbon in carbonnanotubes to carbide nanorods can be controlled by adjusting theconcentration of the Q-containing compound, the temperature at which thereaction occurs and the duration of the exposure of carbon nanotubes tothe volatile Q-containing compound. The extent of conversion of thecarbon from the carbon nanotubes is between 0.5% and 100%, andpreferably around 95%. The resulting carbide nanorods have an excellentpurity level in the carbide content, vastly increased surface area andimproved mechanical strength. The surface area of the carbide nanorodsis from 1 to 400 and preferably 10 to 300 m²/gm.

[0113] Applications for compositions based on carbide nanorods includecatalysts and catalyst supports. For example, compositions includingcarbide nanorods based on molybdenum carbide, tungsten carbide, vanadiumcarbide, tantalum carbide and niobium carbide are useful as catalysts influid phase reactions.

[0114] Similarly, silicon carbide and aluminum carbide-containingnanorods are especially useful as catalyst supports for conventionalcatalysts such as platinum and palladium, as well as for otherQ-containing carbides such as molybdenum carbide, tungsten carbide,vanadium carbide and the like.

[0115] Oxycarbide Nanorods

[0116] Oxycarbide-containing nanorods can be prepared from carbidenanorods. The carbide nanorods are subjected to oxidative treatmentsknown in the art. For example, oxidative treatments are disclosed inU.S. Pat. No. 5,576,466; M. Ledoux, et al. European Pat. Appln. No. 0396475 A1, 1989; C. Pham-Huu, et al., Ind. Eng. Chem. Res. 34, 1107-1113,1995; E. Iglesia, et al., Journal of Catalysis, 131,523-544, 1991. Theforegoing oxidative treatments are applicable to the formation ofoxycarbide nanorods as well as to the formation of nanotubes and/ornanorods comprising an oxycarbide portion wherein the conversion of thecarbide source is incomplete.

[0117] Oxycarbide compounds present in an oxycarbide nanorod, and alsopresent when the conversion of the carbide source is incomplete, includeoxycarbides having a total amount of oxygen sufficient to provide atleast 25% of at least 1 monolayer of absorbed oxygen as determined bytemperature programmed desorption (TPD) based on the carbide content ofthe carbide source. For example, by subjecting carbide nanorods to acurrent of oxidizing gas at temperatures of between 30° C. to 500° C.oxycarbide nanorods are produced. Useful oxidizing gases include but arenot limited to air, oxygen, carbon dioxide, nitrous oxide, water vaporand mixtures thereof. These gases may be pure or diluted with nitrogenand/or argon.

[0118] Compositions comprising oxycarbide nanorods are useful ascatalysts in many fluid phase petrochemical and refining processesincluding hydrogenation, hydrodesulfurisation, hydrodenitrogenation,hydrodemetallisation, hydrodeoxygenation, hydrodearomatization,dehydrogenation, hydrogenolysis, isomerization, alkylation, dealkylationand transalkylation.

[0119] Supported Carbides and Oxycarbides

[0120] According to another embodiment of the present invention, byadjusting the process parameters, for example, the temperature, theconcentration of, and the length of exposure to the Q-containingvolatile compound, it is possible to limit the rate of conversion of thecarbon in the carbon nanotube. Thus, it is possible to provide carbonnanotubes having a carbide portion where the location of the carbideportion can be engineered as desired. For example, the carbide portionof the carbon nanotube can be located entirely on the surface of thecarbon nanotube such that only parts of the surface comprise nanocarbidecompounds. It is possible to have the entire surface of the carbonnanotube coated with carbides while the core of the carbon nanotuberemains substantially carbon. Moreover, it is possible to control thesurface coverage of carbon nanotubes with carbide compounds at from 1%to 99% of the entire surface area. An embodiment wherein the carbonnanotube comprises carbide covering less than 50% of the surface of thecarbon nanotube is preferred. Of course, at low percentages large areasof the carbon nanotube surface remain uncovered. Nevertheless, as longas the carbide portion of the carbon nanotube is retained at thesurface, the morphology of the carbon nanotube remains substantially thesame. Similarly, through careful control of the process parameters, itis possible to turn the carbide portion of the nanotube into a carbidenanorod thereby obtaining a nanotube-nanorod hybrid structure. Thecarbide portion can be located anywhere on the carbon nanotube. Partialconversion of carbon to carbide compounds preferably varies from about20% to about 85% by weight. When the content of carbide compounds in thecarbon nanotube exceeds 85% by weight, the carbon nanotubes have beensubstantially converted to carbide nanorods. Once in possession of theteachings herein, one of ordinary skill in the art can determine as aroutine matter and without the need for undue experimentation how tocontrol the rate of conversion of carbon nanotubes to carbide nanorodsin order to convert the carbon in the carbon nanotubes incompletely.

[0121] The embodiment of the invention where the carbon nanotubescontain a carbide portion also encompasses providing the carbide portionof the carbon nanotube in any manner now known or later developed. Forexample, in another method of providing carbide compounds on carbonnanotubes or aggregates thereof, the Q-containing metal or metalcompound, preferably molybdenum, tungsten, or vanadium is placed on thecarbon nanotubes or aggregates directly and then pyrolyzed, leavingbehind carbon nanotubes coated with carbide compounds.

[0122] In yet another method of providing carbide compounds on carbonnanotubes, solutions of Q-containing salts, such as, for example, saltsof molybdenum, tungsten, or vanadium are dispersed over the carbonnanotubes or aggregates thereof and then pyrolyzed, again formingcarbide compounds primarily on the surface of the carbon nanotubes.

[0123] An embodiment wherein the core of the carbon nanotube remainscarbon and the location of the metallic carbides is limited is quitedesirable as a catalytic system. The core of the carbon nanotube acts asa catalyst support or carrier for the metallic carbide catalyst.

[0124] In yet another embodiment of the improvement discussed above, itis possible to subject the nanotube having a carbide portion tooxidative treatments such that the carbide portion of the nanotubefurther comprises an oxycarbide portion. The oxycarbide portioncomprises oxycarbide compounds located any place on, in and within thecarbon nanotube or carbide nanorod.

[0125] The oxycarbide compounds can be placed on the nanotube in any waynow known or later developed. Similarly, the nanotube having a carbideportion can be exposed to air or subjected to carburization or any othermeans of converting the carbide portion of the nanotube partially orcompletely into an oxycarbide nanorod portion. Thus, it is possible toprovide a carbon nanotube which is partly still a carbon nanotube,partly a carbide nanorod and partly an oxycarbide nanorod. This may bereferred to as a carbon-carbide-oxycarbide nanotube-nanorod hybrid.

[0126] Carbide and Oxycarbide Rigid Porous Structures

[0127] The invention also relates to rigid porous structures made fromcarbide nanorods, oxycarbide nanorods, and supported carbide andoxycarbide carbon nanotubes and methods for producing the same. Theresulting structures may be used in catalysis, chromatography,filtration systems, electrodes, batteries and the like.

[0128] The rigid porous structures according to the invention have highaccessible surface area. That is, the structures have a high surfacearea which is substantially free of micropores. The invention relates toincreasing the mechanical integrity and/or rigidity of porous structurescomprising intertwined carbon nanotubes and/or carbide and/or oxycarbidenanorods. The structures made according to the invention have highercrush strengths than the conventional carbon nanotube or nanorodstructures. The present invention provides a method of improving therigidity of the carbon structures by causing the nanotubes and/ornanorods to form bonds or become glued with other nanotubes and/ornanorods at the nanotube and/or nanorod intersections. The bonding canbe induced by chemical modification of the surface of the nanotubes topromote bonding, by adding “gluing” agents and/or by pyrolyzing thenanotubes to cause fusion or bonding at the interconnect points.

[0129] The nanotubes or nanorods can be in the form of discretenanotubes and/or nanorods or aggregate particles of nanotubes andnanorods. The former results in a structure having fairly uniformproperties. The latter results in a structure having two-tieredarchitecture comprising an overall macrostructure comprising aggregateparticles of nanotubes and/or nanorods bonded together and amicrostructure of intertwined nanotubes and/or nanorods within theindividual aggregate particles.

[0130] According to one embodiment, individual discrete nanotubes and/ornanorods form the structure. In these cases, the distribution ofindividual nanotube and/or nanorod strands in the particles aresubstantially uniform with substantially regular spacing betweenstrands. These spacings (analogous to pores in conventional supports)vary according to the densities of the structures and range roughly from15 nm in the densest to an average 50 to 60 nm in the lightest particles(e.g., solid mass formed from open net aggregates). Absent are cavitiesor spaces that would correspond to micropores in conventional carbonsupports.

[0131] According to another embodiment, the distribution of individualnanotubes and/or nanorods is substantially nonuniform with asubstantially nonuniform pore structure. Nevertheless, there are nocavities or spaces corresponding to micropores which are frequentlypresent in other catalysts and catalyst supports.

[0132] These rigid porous materials are superior to currently availablehigh surface area materials for use in fixed-bed reactors, for example.The ruggedness of the structures, the porosity (both pore volume andpore structure), and the purity of the carbide nanorods and/oroxycarbide nanorods are significantly improved. Combining theseproperties with relatively high surface areas provides a unique materialwith useful characteristics.

[0133] One embodiment of the invention relates to a rigid porousstructure comprising carbide nanorods having an accessible surface areagreater than about 10 m²/gm and preferably greater than 50 m²/gm, beingsubstantially free of micropores and having a crush strength greaterthan about 1 lb. The structure preferably has a density greater than 0.5gm/cm³ and a porosity greater than 0.8 cm³/gm. Preferably, the structurecomprises intertwined, interconnected carbide nanorods and issubstantially free of micropores.

[0134] According to one embodiment, the rigid porous structure includescarbide nanorods comprising oxycarbide compounds, has an accessiblesurface area greater than about 10 m²/gm, and preferably greater than 50m²/gm, is substantially free of micropores, has a crush strength greaterthan about 1 lb and a density greater than 0.5 gm/cm³ and a porositygreater than 0.8 cm³/gm.

[0135] According to another embodiment the rigid porous structureincludes oxycarbide nanorods having an accessible surface area greaterthan about 10 m²/gm, and preferably greater than 50 m²/gm, beingsubstantially free of micropores, having a crush strength greater thanabout 1 lb, a density greater than 0.5 gm/cm³ and a porosity greaterthan 0.8 cm³/gm.

[0136] According to yet another embodiment, the rigid porous structureincludes carbon nanotubes comprising a carbide portion. The location ofthe carbide portion can be on the surface of the carbon nanotube or anyplace on, in or within the carbon nanotube or the carbide portion can beconverted into a carbide nanorod forming a carbon nanotube-carbidenanorod hybrid. Nevertheless, the catalytic effectiveness of these rigidporous structures is not affected by the carbide portion on theresulting composites. This rigid porous structures has an accessiblesurface area greater than about 10 m²/gm and preferably than 50 m²/gm,is substantially free of micropores, has a crush strength greater thanabout 1 lb, a density greater than 0.5 gm/cm³ and a porosity greaterthan 0.8 cm³/gm.

[0137] In another related embodiment the rigid porous structure includescarbon nanotubes having a carbide portion and also an oxycarbideportion. The location of the oxycarbide portion can be on the surface ofthe carbide portion or any place on, in or within the carbide portion.

[0138] Under certain conditions of oxidative treatment it is possible toconvert a portion of the carbide nanorod part of the carbon-carbidenanotube-nanorod hybrid into an oxycarbide. The rigid porous structureincorporating carbon-carbide-oxycarbide nanotube-nanorod hybrids has anaccessible surface area greater than about 10 m^(b 2)/gm, issubstantially free of micropores, has a crush strength greater thanabout 1 lb, a density greater than 0.5 gm/cm³ and a porosity greaterthan 0.8 cm³/gm.

[0139] According to one embodiment, the rigid porous structuresdescribed above comprise nanotubes and/or nanorods which are uniformlyand evenly distributed throughout the rigid structures. That is, eachstructure is a rigid and uniform assemblage of nanotubes and/ornanorods. The structures comprise substantially uniform pathways andspacings between the nanotubes and/or nanorods. The pathways or spacingsare uniform in that each has substantially the same cross-section andare substantially evenly spaced. Preferably, the average distancebetween nanotubes and/or nanorods is less than about 0.03 μm and greaterthan about 0.005 μm. The average distance may vary depending on thedensity of the structure.

[0140] According to another embodiment, the rigid porous structuresdescribed above comprise nanotubes and/or nanorods which arenonuniformly and unevenly distributed throughout the rigid structures.The rigid structures comprise substantially nonuniform pathways andspacings between the nanorods. The pathways and spacings have nonuniformcross-section and are substantially unevenly spaced. The averagedistance between nanotubes and/or nanorods varies between 0.0005 μm to0.03 μm. The average distances between nanotubes and/or nanorods mayvary depending on the density of the structure.

[0141] According to another embodiment, the rigid porous structurecomprises nanotubes and/or nanorods in the form of nanotube and/ornanorod aggregate particles interconnected to form the rigid structures.These rigid structures comprise larger aggregate spacings between theinterconnected aggregate particles and smaller nanotube and/or nanorodspacings between the individual nanotubes and/or nanorods within theaggregate particles. Preferably, the average largest distance betweenthe individual aggregates is less than about 0.1 μm and greater thanabout 0.001 μm. The aggregate particles may include, for example,particles of randomly entangled balls of nanotubes and/or nanorodsresembling bird nests and/or bundles of nanotubes and/or nanorods whosecentral axes are generally aligned parallel to each other.

[0142] Another aspect of the invention relates to the ability to providerigid porous particulates or pellets of a specified size dimension. Forexample, porous particulates or pellets of a size suitable for use in afluidized packed bed. The method involves preparing a plurality ofnanotubes and/or nanorods aggregates, fusing or gluing the aggregates ornanotubes and/or nanorods at their intersections to form a large rigidbulk solid mass and sizing the solid mass down into pieces of rigidporous high surface area particulates having a size suitable for thedesired use, for example, to a particle size suitable for forming apacked bed.

[0143] General Methods of Making Rigid Porous Structures

[0144] The above-described rigid porous structures are formed by causingthe nanotubes and/or nanorods to form bonds or become glued with othernanofibers at the fiber intersections. The bonding can be induced bychemical modification of the surface of the nanofibers to promotebonding, by adding “gluing” agents and/or by pyrolyzing the nanofibersto cause fusion or bonding at the interconnect points. U.S. Pat. No.6,099,965 to Tennent describes processes for forming rigid porousstructures from carbon nanotubes. These processes are equally applicableto forming rigid porous structures including discrete unstructurednanotubes or nanotube aggregates comprising carbides and in anotherembodiment also oxycarbides, wherein the carbon nanotube morphology hasbeen substantially preserved. These methods are also applicable toforming rigid porous structures comprising carbide or oxycarbidenanorods, unstructured or as aggregates. Additionally, these methods arealso applicable to forming rigid porous structures comprising hybrids ofcarbon-carbide nanotube-nanorods and/or carbon-carbide-oxycarbidenanotube-nanorods.

[0145] In several other embodiments rigid porous structures comprisingcarbide nanorods are prepared by contacting a rigid porous carbonstructure made of carbon nanotubes with volatile Q-containing compoundsunder conditions sufficient to convert all of the carbon or only part ofthe carbon of the carbon nanotubes to carbide-containing compounds.

[0146] Methods of Making Carbide Containing Rigid Porous Structures

[0147] There are many methods of preparing rigid porous structurescomprising carbide nanorods. In one embodiment the rigid porous carbonstructures prepared as described above are contacted with Q-containingcompounds under conditions of temperature and pressure sufficient toconvert the carbon nanotubes of the rigid porous carbon structure tocarbide nanorods. The carbide portion of the carbon nanotubes of therigid porous structure can be on the surface of the carbon nanotube orat any place on, in or within the carbon nanotube. When the conversionis complete, the entire carbon nanotube is transformed into asubstantially solid carbide nanorod. Once in the possession of theteachings herein, one of ordinary skill in the art can determine as aroutine matter and without the need for undue experimentation how tocontrol the rate of conversion of carbon nanotubes present in the rigidporous carbon structure to a rigid porous carbide-containing structurecomprising carbon nanotubes having a carbide portion located at variousplaces on the carbon nanotube present in an amount from about 20% toabout 85%, preferably in excess of 85% by weight.

[0148] The carbide-containing rigid porous structures of the presentinvention have high accessible surface areas between 10 m²/gm and 100m²/gm and are substantially free of micropores. These structures haveincreased mechanical integrity and resistance to attrition in comparisonto individual carbide-containing nanorods. Carbide-containing rigidporous structures have a density greater than 0.5 gm/cm³ and a porositygreater than 0.8 cm³/gm. The structure has at least two dimensions of atleast 10 μm and not greater than 2 cm. Depending on the pore structureof the starting rigid porous carbon structure, the structure of thecarbide-containing rigid porous structure can be uniform, nonuniform orbimodal.

[0149] When the rigid porous structure is uniform the average distancebetween the carbide-containing nanorods is less than 0.03 μm and greaterthan 0.005 μm. In another embodiment the rigid porous structurecomprises carbide-containing nanorods in the form of interconnectedaggregate particles wherein the distance between individual aggregatesranges from point of contact to 1 μm. When the carbide-containingnanorod rigid porous structures are formed from rigid porous carbonstructures comprising nanotube aggregates, the structure has aggregatespacings between interconnected aggregate particles and carbide nanorodspacings between nanorods within the aggregate particles. As a resultthe rigid porous structure has a bimodal pore distribution.

[0150] One embodiment of the invention relates to rigid porousstructures comprising extrudates of aggregate particles of carbidenanorods, wherein the carbide nanorods are glued together with bindingagents such as cellulose, carbohydrates, polyethylene, polystyrene,nylon, polyurethane, polyester, polyamides, poly(dimethylsiloxane) andphenolic resins. Without being bound by theory, it is believed that theconversion of a rigid porous carbon structure to a carbide-containingrigid porous structure, whether completely or partially, is accomplishedin pseudotopotactic manner as previously discussed.

[0151] Methods of Making Oxycarbide Containing Rigid Porous Structures

[0152] There are many methods of preparing rigid porous structurescomprising oxycarbide nanorods and/or nanotubes comprising a carbideportion and an oxycarbide portion. In one embodiment the carbidecontaining rigid porous structures are subjected to oxidative treatmentsas disclosed in the art and in U.S. Pat. No. 5,576,466.

[0153] In another embodiment rigid porous structures comprising carbonnanotubes having an oxycarbide portion and/or a carbide portion areprepared by subjecting rigid porous carbon structures which have beenpartially converted to carbide nanorods to oxidative treatmentsdisclosed in the art.

[0154] In another embodiment discrete carbide nanorods are subjected tooxidative treatments and then assembled into rigid porous structuresaccording to methods similar to those disclosed in U.S. Pat. No.6,099,965.

[0155] In yet another embodiment discrete carbon nanotubes or aggregateof carbon nanotubes which have been partially converted to carbidenanorods are further subjected to oxidative treatments and thenassembled into rigid porous structures according to methods disclosed inU.S. Pat. No. 6,099,965.

[0156] Catalytic Compositions

[0157] The carbide and/or oxycarbide nanorods and nanotubes havingcarbide and/or oxycarbide portions of the invention, have superiorspecific surface areas as compared to carbide and oxycarbide catalystspreviously taught in the art. As a result, they are especially useful inthe preparation of catalysts and as catalyst supports in the preparationof supported catalysts. The catalysts of the invention include catalyticcompositions comprising nanotubes and/or nanorods and rigid porousstructures comprising the same. These “self-supported” catalysts of theinvention constitute the active catalyst compound and can be used withor without any additional physical support to catalyze numerousheterogeneous, fluid phase reactions as more specifically describedherein. The supported catalysts of the invention comprise a supportincluding a nanofiber and/or nanorod rigid porous structure and acatalytically effective amount of a catalyst supported thereon. Thecatalytic compositions can contain from about 10% to 95% carbides byweight of the composition. The catalyst compositions can further includefrom about 0.5% to 25% oxycarbides by weight of the carbides of thecomposition.

[0158] The uniquely high macroporosity of carbon nanotube or carbidenanorod structures, the result of their macroscopic morphology, greatlyfacilitates the diffusion of reactants and products and the flow of heatinto and out of the self-supported catalysts. This unique porosityresults from a random entanglement or intertwining of nanotubes and/ornanorods that generates an unusually high internal void volumecomprising mainly macropores in a dynamic, rather than static state.Ease of separation of these catalysts from the fluid phase and lowerlosses of these catalyst as fines also improves process performance andeconomics. Other advantages of the nanotube and/or nanorod structures asself-supported catalysts include high purity, improved catalyst loadingcapacity and chemical resistance to acids and bases. As self-supportedcatalysts, carbon nanotube and/or nanorod aggregates have superiorchemical and physical properties in respect of their porosity, surfacearea, separability and purity.

[0159] Self-supported catalysts made of nanotubes and/or nanorods have ahigh internal void volume that ameliorates the plugging problemencountered in various processes. Moreover, the preponderance of largepores obviates the problems often encountered in diffusion or masstransfer limited reactions. The high porosities ensure significantlyincreased catalyst life.

[0160] One embodiment of the invention relates to a self-supportedcatalyst which is a catalytic composition comprising carbide-containingnanorods having a diameter between at least 1 nm and less than 100 nm,and preferably between 3.5 nm and twenty nm. The carbide-containingnanorods have been prepared from carbon nanotubes which have beensubstantially converted to carbide nanorods. In the catalyticcompositions of this embodiment the carbide nanorods retainsubstantially the structure of the original carbon nanotubes. Thus, thecarbide nanotubes can have uniform, nonuniform or bimodal porousstructures. These catalytic compositions can be used as catalysts tocatalyze reactions such as hydrogenation, hydrodesulfurisation,hydrodenitrogenation, hydrodemetallisation, hydrodeoxygenation,hydrodearomatization, dehydrogenation, hydrogenolysis, isomerization,alkylation, dealkylation and transalkylation.

[0161] Catalytic Compositions Supported on Aggregates of Carbide andOxycarbide Nanorods

[0162] Depending upon the application, the rigid porous structures ofthe invention can be used as both self-supported catalysts and ascatalyst supports. As is true of catalysts comprising regular nanotubesand/or nanorods, catalysts and catalyst supports comprising the rigidporous structures of the invention have unique properties. They arerelatively free of micropores. They are also pure and resistant toattrition, compression and shear. Consequently, they can be easilyseparated from a fluid phase reaction medium and after a long servicelife. The rigid porous structures of the invention can be used ascatalysts and catalyst supports in a variety of fixed bed catalyticreactions.

[0163] Rigid structures formed from nanorod aggregates, preferablysilicon carbide and aluminum carbide-containing nanorods, areparticularly preferred structures for use as catalyst supports.

[0164] The combination of properties offered by nanorod structures isunique. Known catalyst supports do not have such high porosity, highaccessible surface area and attrition resistance. This combination ofproperties is advantageous in any catalyst system amenable to the use ofa carbide catalyst support. The multiple nanorods that make up a nanorodstructure provide a large number of junction points at which catalystparticles can bond to the structures. This provides a catalyst supportthat tenaciously holds the supported catalyst. Further, nanorodstructures permit high catalyst loadings per unit weight of nanorod.Catalyst loadings are generally greater than 0.01 weight percent andpreferably greater than 0.1, but generally less than 5% weightcontaining on the total weight of the supported catalyst. Typicallycatalyst loadings greater than 5% by weight are not useful, but suchcatalyst loadings are easily within the contemplation of the invention,as are loadings in excess of 50 weight percent containing of the totalweight of the supported catalyst.

[0165] Desirable hydrogenation catalysts which can be supported on thenanorod and/or nanotube structures of the invention are the platinumgroup of metals (ruthenium, osmium, rhodium, iridium, palladium andplatinum or a mixture thereof), preferably palladium and platinum or amixture thereof. Group VII metals including particularly iron, nickeland cobalt are also attractive hydrogenation catalysts.

[0166] Oxidation (including partial oxidation) catalysts may also besupported on the nanotube and/or nanorod structures. Desirable metallicoxidation catalysts include, not only members of the platinum groupenumerated above, but also, silver and the group VIII metals. Oxidationcatalysts also include metal salts known to the art including salts ofvanadium, tellurium, manganese, chromium, copper, molybdenum andmixtures thereof as more specifically described in HeterogeneousCatalytic Reactions Involving Molecular Oxygen, by Golodets, G. I. &Ross, J. R. H, Studies in Surface Science, 15, Elsevier Press, NYC 1983.

[0167] Active catalysts include other carbide compounds such as carbidesof titanium, tantalum, hafnium, niobium, zirconium, molybdenum, vanadiumand tungsten. These carbides are particularly useful for hydrogenation,hydrodesulfurisation, hydrodenitrogenation, hydrodemetallisation,hydrodeoxygenation, hydrodearomatization, dehydrogenation,hydrogenolysis, isomerization, alkylation, dealkylation andtransalkylation.

[0168] Because of their high purity, carbide nanorod aggregates exhibithigh resistance to attack by acids and bases. This characteristic isadvantageous since one path to regenerating catalysts is regenerationwith an acid or a base. Regeneration processes can be used which employstrong acids or strong bases. This chemical resistance also allows thecarbide supports of the invention to be used in very corrosiveenvironments.

[0169] Preparation of Supported Catalysts

[0170] Supported catalysts are made by depositing a catalyticallyeffective amount of catalyst on the rigid nanorod and/or nanotubestructure. The term “on the nanotube and/or nanorod structure” embraces,without limitation, on, in and within the structure and on the nanotubesand/or nanorods thereof. These terms may be used interchangeably. Thecatalyst can be incorporated onto the nanotube and/or nanorod oraggregates before the rigid structure is formed, while the rigidstructure is forming (i.e., it can be added to the dispersing medium) orafter the rigid structure is formed.

[0171] Methods of depositing the catalyst on the support includeadsorption, incipient wetness, impregnation and precipitation. Supportedcatalysts may be prepared by either incorporating the catalyst onto theaggregate support or by forming it in situ and the catalyst may beeither active before it is deposited in the aggregate or it may beactivated in situ.

[0172] Catalysts such as a coordination complexes of catalytictransition metals, e.g., palladium, rhodium or platinum, and a ligand,such as a phosphine, can be adsorbed on a support by slurrying nanorodsin a solution of the catalyst or catalyst precursor for an appropriatetime to achieve the desired loading.

[0173] These and other methods may be used in forming the catalystsupports. A more detailed description of suitable methods for makingcatalyst supports using nanotube structures is set forth in U.S. Pat.No. 6,099,965.

[0174] Catalytic Compositions and Their Uses

[0175] The above described catalytic compositions are suited for use influid phase reactions such as hydrogenation, hydrodesulfurisation,hydrodenitrogenation, hydrodemetallisation, hydrodeoxygenation,protonation, hydrodearomatization, dehydrogenation, hydrogenolysis,isomerization, alkylation, dealkylation, and transalkylation.

[0176] Modification of Catalytic Compositions

[0177] Catalytic compositions based on carbon nanotubes or carbidenanorods containing carbides and/or oxycarbides can be further modifiedto create catalytic compositions that are bifunctional. For example, inan embodiment of the invention, the catalytic composition containsmultiple active sites. One active site can catalyze a hydrogenation ordehydrogenation reaction. Another active site can catalyze protonationor isomerization reactions. These sites can be created, for example, byan acidification treatment using a strong acid. The term “strong acid”refers to the capability of the reagent to intensely attract electrons.

[0178] Catalysts containing carbide nanorods that include carbidesand/or oxycarbides or containing carbon nanotubes that include carbidesand/or oxycarbides can be modified by acidification. Acidification ofthese catalysts can be accomplished by the incorporation of electronacceptors into the carbon portion of the carbon nanotubes or carbidenanorods, the carbide portion of the carbon nanotubes or carbidenanorods, the oxycarbide carbon nanotubes or carbide nanorods, or anycombination thereof. Thus, the acidic sites can reside on the carbonportions and/or the carbide portions and/or the oxycarbide portions.Examples of electron acceptors include, but are not limited to,halogens, nitrogen, sulfur and phosphorus.

[0179] In an embodiment of the invention, acidification of the catalyticcompositions is accomplished by halogenation. Suitable halogens includefluorine, chlorine, bromine, or iodine. The halogen can also beincorporated using a compound or ion containing a halogen, e.g., ClO₃ ⁻,HCl, CCl₄, CHCl₃, or AlCl₃, etc.

[0180] Prior to the acidification treatment, samples of Q-containingcarbides, for example molybdenum carbide or tungsten carbide, can befirst passivated, or oxygenated, by oxygen. For example, a gas ratio of3% oxygen and 97% argon can be passed over the samples in order topassivate them. As a result, a minor component of QO₂, or QO/_(x)wherein x is between 1 and 3, is present in the Q-containing carbidesamples.

[0181] The Q-containing carbide can be placed in a micro-reactor or anautoclave reactor. The reaction temperature can be raised to atemperature at which the samples are dried. The temperature can rangefrom about 110° C. to about 300° C., e.g., 200° C. During the dryingprocess, the samples are blanketed under argon. The argon blanket isthen replaced by a carrier gas that contains from about 0.5% to about10% of Cl₂. The carrier gas chlorinates the samples. The chlorinationprocedure should be carried out under Cl₂/Ar at temperatures in therange of 500° C. to 850° C., e.g., 600° C. for, e.g. 1 hour.

[0182] Carbon tetrachloride can be used to chlorinate the samples. Whenusing CCl₄ to chlorinate, argon is passed through a gas-liquid saturatorthat contains pure CCl₄. The temperature of the saturator should be keptat 0° C. by, for example, an ice-water bath. The chlorination procedureis then performed under CCl₄/Ar vapor at 200 to 300° C. for a period oftime, e.g. 1 hour.

[0183] Before the chlorination procedure, the samples can also be heatedin hydrogen at a temperature up to about 500° C. to remove the surfaceoxygen atoms and create anion vacancies to facilitate furtherincorporation of chlorine. After the hydrogen treatment, the sample ischlorinated.

[0184] In another embodiment of the invention, sulfation is used. Anycompound capable of sulfation can be used, e.g., a sulfate or persulfatecontaining compound.

[0185] Instead of modifying the surface of the catalyst supports, themodification can be made directly to the carbide phase of theQ-containing catalysts. For example, the carbide phases of theQ-containing catalysts can be treated with an acidifying compound. Thetreatment results in the substitution of halogen, nitrogen, phosphorus,and/or oxygen into the carbide structure of the Q-containing catalysts.A skin is formed having a formula of MoCl_(x), MoO_(x)Cl_(y), MoN_(x),MoO_(x)N_(y), MoP_(x), or MoO_(x)C_(y) where x and y are indefinitenumbers representing stoichiometric or non-stochiometric compositions.The presence of the skin alters the acidity of the Q-containingcatalyst.

[0186] For example to acidify the carbide phase of a Q-containingcatalyst, nitrogen from NH₃ can be used by heating the NH₃ with theQ-containing catalyst to a temperature from 500° C. to 850° C.

[0187] In yet another embodiment of the invention acidification of thecatalytic compositions can be accomplished by the addition of solidacids into the interstitial positions between the carbon nanotubes andsupported carbides. Alternatively, the solid acids can be physicallyincorporated onto the surface of the rigid porous structures formed fromcarbide nanorods or nanotubes. The term “solid acid” refers to solidLewis Acids. Examples of solid acids include, but are not limited to,chlorinated, sulfated, or phosphated compounds containing aluminum orzirconium. The solid acids can be incorporated into the catalyticcompositions by incipient wetness or other appropriate technique knownin the art. The solid acids can be incorporated before or aftercalcination.

[0188] Modified catalytic compositions are suitable for use in fluidphase reactions including, but not limited to, hydrogenation,hydrodesulfurisation, hydrodenitrogenation, hydrodemetallisation,hydrodeoxygenation, hydrodearomatization, dehydrogenation,hydrogenolysis, protonation, isomerization, alkylation, dealkyation andtransalkylation. For example, the modified catalytic compositions can beused in the isomerization of alkanes, e.g., butane.

[0189] The acidities of the modified catalytic compositions can bemeasured by means known in the art. For example, temperature programmeddesorption can be used. Temperature programmed desorption is a techniqueused to examine the surface properties of solid materials. Typically, asmall amount of catalyst (10-200 mg) is placed in a reactor that can beheated by a furnace. An inert gas, usually helium or argon atatmospheric pressure, is passed over the catalyst. Followingpretreatment to obtain a “clean” catalyst, a gas is adsorbed on thesurface, usually by pulse injections of adsorbate into the carrier gasupstream of the reactor. After excess gas is flushed out, the catalystis heated at a rate such that its temperature rises linearly with time.A small thermocouple inserted in the catalyst measures the temperatureand a detector downstream measures the change in the inert gas stream.The ideal detector is a mass spectrometer which measures the compositionof the effluent stream as a function of catalyst temperature. Because ofthe high carrier gas flow rate, the detector response is proportional tothe rate of desorption if diffusion and reabsorption are not limiting.By adsorbing acidic or basic gas molecules followed by desorbing uponheating, one can measure the intensity and quantity of the adsorptionand thereby characterize the surface properties such as acidity orbasicity. Ammonia is a molecule commonly used to measure the acidity ofa solid surface. A weak acid usually desorbs at approximately 100° C.and a strong acid usually desorbs at temperatures higher than 100° C.Strong acidity is also associated with large quantities of adsorption ofammonia.

[0190] Isomerization Reactions Using Modified Carbide or OxycarbideCatalysts

[0191] Modified carbide and/or oxycarbide catalysts can use advantagesto use to catalyze isomerization reactions, such as the isomerization ofalkanes. Any straight-chain, branched or cyclic alkane can be employedas a feed hydrocarbon in the isomerization process. Examples of alkaneswhich can be isomerized include, but are not limited to, n-butane,n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane,2-methylhexane, 3-methylhexane, octanes, nonanes, decanes andcombinations thereof. Alkenes, or olefins, can also be isomerized usingthe catalysts.

[0192] Any suitable isomerization conditions can be employed in theprocess of the invention. A feed hydrocarbon and a carrier gas such ashydrogen are premixed to create an isomerization feed stream which isthen charged to an isomerization zone, i.e., a vapor phase reactorvessel. The feed stream contacts a modified catalytic composition of theinvention that has been placed within the reactor vessel.

[0193] The effluent from the reactor vessel is subjected to suitableseparation techniques as known in the art, to separate the desiredisomer product from reactants and by-products.

[0194] For example, in the isomerization of normal butane to isobutane,the following process can be used. A vapor phase reactor can beconstructed by assembling a thermowell through an end of a verticalquartz tube. A vertical quartz tube with a 12 mm outer diameter can befitted with a 6 mm quartz thermowell. At the tip of the thermowell, is aporous plug of quartz wool. This porous plug can be used to support thecatalyst and/or the catalyst support containing the catalyst. The entiretube is then placed in a tube furnace, for example a ½-inch tubefurnace, in a vertical orientation. The top of the tube is fitted withinlet lines for the feed stream of reactant gases. At the bottom of thetube is an exit line connected to a pressure gauge, e.g., a gaugemeasuring pressure between 0 and 15 psi. Mass flow controllers areplaced in the gas inlet lines to control the flow of reactant gases intothe reactor. Suitable mass flow controllers include those manufacturedby Allborg Instruments and Controls of Orangeburg, N.Y.

[0195] Ground catalyst or supported catalyst is placed onto the quartzwool plug. The catalytic composition is then treated with hydrogen andargon gas. Thereafter, the catalytic composition can be treated withoxygen and argon gas.

[0196] Mixtures of the gas to be isomerized, e.g., n-butane, andhydrogen in molar ratios of about 1:16 to 1:4 of n-butane:H₂ areintroduced into the vapor phase reactor at WHSVs of 1-10 h⁻¹.Temperatures and pressures for the reaction can range from 100° C. toabout 400° C., and 1 to about 10 psi, respectively.

[0197] Product gases are fed through a gas sampling valve. Gaschromatography (“GC”) can be used to analyze the composition of theproduct gas and determine the conversion and selectivity of thereaction. For example, a Varian gas chromatograph equipped with a GS-Qcapillary column can be used to measure C₁-C₅ alkanes and olefins. Thecapillary columns can be obtained from Alltech Associates of Deerfield,Ill.

EXAMPLES

[0198] The examples are illustrative and not to be consideredrestrictive of the scope of the invention. Numerous changes andmodification can be made with respect to the invention. The materialsused in the examples herein are readily commercially available.

[0199] In all of the experiments which follow, aggregates of carbonnanotubes as manufactured by Hyperion Catalysis International ofCambridge, Mass. were used. The aggregates of carbon nanotubes were ofthe cotton candy (“CC”) morphology also known as combed yarn (“CY”) asdescribed in the section entitled “Nanotube Aggregates and Assemblages”.

Example 1

[0200] Preparation of Molybdenum Carbide Precursors by Impregnation ofCarbon Nanotube Aggregates with Molybdenum Acetyl Acetonate

[0201] Five gms of powder samples of CC aggregates having porosity of6.5 cc/gm were impregnated by the incipient wetness method with 35 cc ofan ethanol solution containing the correct amount of MoO₂(C₅ H₇ O₂)₂ or(molybdenum acetyl acetonate, referred to as Moacac) necessary for thedesired C:Mo atom ratio loading. The resulting mixture was dried at 110°C. at full vacuum for 18 hours during which the Mo precursor decomposedto a mixture of molybdenum suboxides, generally designated as MoO_(3−x),wherein x is 0 or 1. The sample was set aside for conversion to carbidecatalysts by careful calcination under an inert atmosphere as describedin Examples 5, 6 or 7 below.

Example 2

[0202] Preparation of Molybdenum Carbide Precursors by Impregnation ofCarbon Nanotube Aggregates with Ammonium Molybdate

[0203] A similar procedure as used in Example 1 above was followed,except that the impregnating solutions were aqueous solutions containingthe correct amount of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄.4H₂O, referred to as ammonium molybdate) necessary for the desiredC:Mo atom ratio loading. The resulting mixtures were dried at 225° C. infull vacuum for 18 hours during which the heptamolybdate compound wasdecomposed to MoO₃. The sample was set aside for conversion to carbidecatalysts by careful calcination under an inert atmosphere as moreparticularly described in Examples 5, 6 and 7 herein.

Example 3

[0204] Preparation of Molybdenum Carbide Extrudate Precursors byImpregnation with Molybdenum Acetyl Acetonate or Ammonium Molybdate

[0205] CC or CY type aggregates were oxidized with nitric acid asdescribed in U.S. Pat. No. 6,203,814 to Fischer to form oxidized CCaggregates having an acid titer of about 0.6 meq/gm.

[0206] Five gms of the oxidized CC type aggregates of carbon nanotubeswere well-mixed with either an ethanol solution of Moacac or an aqueoussolution of ammonium heptamolybdate tetrahydrate, each solutioncontaining the correct amount of Mo compound necessary for the desiredC:Mo loading. The mixing was accomplished by kneading in a Braybenderkneader until the paste had a homogeneous consistency. The excesssolvent was removed from the kneaded sample by evaporation until asolids content of from about 8 to about 10% by weight was obtained. Thematerial was then extruded by using a pneumatic gun extruder. Theextrudates were about ⅛″ in diameter and several centimeters in length.The extrudates were then dried at 200° C. in air for 18 hours duringwhich some shrinkage occurred. The dried extrudates were then brokeninto pieces of about {fraction (1/16)}″ by ¼″ which were set aside forconversion to carbide catalysts by careful calcination as described inExamples 5, 6 and 7 herein.

Example 4

[0207] Preparation of Molybdenum Carbide Precursor by Mixing CarbonNanotube Aggregates With Ammonium Molybdate or Molybdenum Oxide

[0208] As grown CC or CY aggregates were oxidized with nitric acid asdescribed in Example 3 to form oxidized CC aggregates having an acidtiter of about 0.6 meq/gm.

[0209] Five gms of oxidized CC type aggregates of carbon nanotubes werephysically admixed with the correct amount of either ammoniumheptamolybdate tetrahydrate or MoO₃ necessary for the desired C:Mo atomratio by kneading the sample in a mortar and pestle. A small amount ofwetting agent such as water or ethylene glycol, was added periodicallyto keep the oxidized carbon nanotube powder dusting under control and tofacilitate the contact between the molybdenum precursor particles andthe carbon nanotube aggregates. After the mix was kneaded to ahomogeneous thick paste, the excess solvent was removed by gentlewarming while continuing to knead the sample. The mixture was then driedat 200° C. for 14 hours in air and set aside for conversion to carbideby careful calcination as described in Examples 5, 6 and 7 herein.

Example 5

[0210] Calcination of Molybdenum Carbide Precursors at 600° C. or 625°C.

[0211] Weighed samples of molybdenum carbide precursors, as prepared inExamples 1-4 were loaded into porcelain boats which were then placedhorizontally in a one-inch quartz tube. The tube and boat assembly wereplaced in a high temperature furnace equipped with a programmabletemperature controller and a movable thermocouple. The thermocouple waslocated directly in contact with the end of the boat. The sample washeated under a slow flow, i.e., at several standard cc's/min of argon ata heating rate of 5° C./min to 200° C. and thereafter at 1° C./min tothe final temperature of 600° C. or 625° C. The sample was held at thistemperature for 18 hours. Since pure Mo₂C reacts violently withatmospheric oxygen, after cooling in argon to ambient temperature, thesamples were passivated by passing 3% O₂/Ar over them for 1 hour. XRDphase analysis indicated that the precursors have converted into β-Mo₂Cand/or γ-Mo₂C with minor component of MoO₂.

Example 6

[0212] Calcination of Molybdenum Carbide Carbon Precursors at 800° C.

[0213] The same procedure as described in Example 5 above was followedup to 600° C. The samples were then held at 600° C. for 1 hour.Thereafter, heating was resumed at the same rate of 1° C./min to 800° C.and held at that temperature for another 3 hours. After cooling inargon, the samples were passivated using 3% O₂/Ar. XRD phase analysisindicated that the precursors have converted into β-Mo₂C.

Example 7

[0214] Calcination of Molybdenum Carbide Carbon Precursors at 1000° C.

[0215] The same procedure as described in Example 6 above was followedup to 800° C., at which temperature the samples were held for 1 hour.Thereafter, heating of the samples was resumed at the rate of 1° C./minto 1000° C., where the temperature was maintained for 0.5 hours. Aftercooling in argon, the samples were passivated using 3% O₂/Ar. XRD phaseanalysis indicated that the precursors have converted into β-Mo₂C.

Results of Examples 1-7

[0216] Carbide nanorods and carbide nanoparticles supported on carbonnanotubes were prepared according to Examples 1 to 7 above. Table 1below summarizes the experimental conditions and XRD results forselected experiments. TABLE 1 SUMMARY OF RESULTS FOR MOLYBDENUM CARBIDEPREPARATIONS C: Mo Weight loss SAMPLE Mo Source T° C. initial (theor.)PHASES, XRD 1 Moacac (s)^(b) 600   4 (94)^(e) 27 (44) C, MoO₂, Mo₂C(hex) 2 MoO₃ (s)^(a) 800  35 (38)^(e) 23 (35) C, Mo₂C (cub) 3 MoO₃(s)^(a) 800  40 (34)^(e) n/a C, Mo₂C (hex) 4 Moacac (s)^(b) 800  10(85)^(e) 31 (32) C, Mo₂C (hex) 5 Moacac (s)^(b) 800  20 (57)^(e) 27 (22)Mo₂C (hex/cub), Mo 6 MoO₃ (s)^(b) 1000  10 (85)^(e) 41 (32) Mo₂C (hex),Mo 7 MoO₃ (s)^(b) 1000  20 (57)^(e) 27 (22) Mo₂C (hex/cub), Mo 8 MoO₃(s)^(b) 1000  10 (85)^(e) 38 (32) C, Mo₂C (hex) 9 MoO₃ (s)^(b) 625  30(43)^(e) 20 (17) C, Mo₂C (hex/cub) 10 MoO₃ (s)^(b) 625  20 (57)^(e) 27(22) C, Mo₂C (hex), MoO₂ 11 MoO₃ (s)^(b) 1000  50 (28)^(e) 12 (11) C,Mo₂C (hex/cub) 12 MoO₃ (s)^(c) 800 3.5 (100)^(e) 55 (55) Mo₂C (hex/cub)

[0217] In the second column is a list of molybdenum precursors convertedto Mo₂C by reaction with carbon nanotubes. Moacac refers to molybdenylacetylacetonate, and MoO₃ refers to molybdenum trioxide. “(s)” refers tothe solid phase of the molybdenum precursor. Superscripts a, b and crefer to methods of dispersing the reactants as described in Examples 2,3 and 4, respectively. T° C. refers to the final calcination temperatureof the reaction temperature cycle. “C:Mo initial ” refers to the atomicratio of C:Mo in the original reaction mixture before conversion to acarbide compound. For example, the stoichiometric atomic ratio toproduce pure carbide with no excess C or Mo, i.e., pure Mo₂C is 3.5. Thenumber following in parentheses is the calculated loading of the Mo₂Ccontained in the resulting materials. “Weight loss (theor.)” refers tothe theoretical weight loss according to the chemical equation. “Phases,XRD” shows the compounds found in the XRD analyses. Mo₂C exists in 2distinct crystallographic phases, hexagonal and cubic. TABLE 2 SUMMARYOF XRD RESULTS Mo₂C Mo₂C Sample (hex) (cubic) MoO₂ MoC >100 nm 1 15˜20nm minor component 2 5˜8 nm 3 5˜8 nm 4 10˜15 nm 5 15˜20 nm 15 nm 6 20 nm7 36˜38 nm 8  8˜10 nm  8˜10 nm 9 18 nm minor component 10 20˜25 nm 5˜8nm 11 35 nm 12 26 nm

[0218] Table 2 summarizes the XRD results for the experiments summarizedin Table 1, identifies the compounds made, the phases present and thecalculated average particle size for different phases.

[0219] The average particle size is a volume-biased average size, suchthat the value of one large particle counts more heavily than severalmedium particles and much more than the volume of many small particles.This is a conventional procedure which is well known to those familiarwith XRD methods.

Discussion of Results of Examples 1-7

[0220] A. Unsupported Mo₂C Nanoparticles and Nanorods

[0221] Samples 1 and 12 provided the clearest evidence of the formationof free-standing Mo₂C nanorods and nanoparticles. These were obtained byreacting stoichiometric or near stoichiometric mixtures of MoO₃ andcarbon nanotubes, either as powder or as extrudates. Productidentification and morphologies were obtained by SEM, HRTEM and XRD. InExample 1, with about 15% excess of carbon, the major product wasidentified by XRD as the hexagonal phase of Mo₂C. MoO₂ and graphiticcarbon were seen as minor components. SEM showed the presence of bothnanorods (approximately 10 to 15 nm in diameter) and nanoparticles(approximately 20 nm).

[0222] Samples 11 and 12 were obtained by reaction carbon nanotubes witheither a stoichiometric mixture of well-dispersed MoO₃ powder or withimpregnated ammonium molybdate. More evidence of the formation of Mo₂Cnanorods and nanoparticles was obtained in Sample 12, obtained byreacting a stoichiometric mixture of MoO₃ and powder of carbonnanotubes. XRD, SEM and HRTEM analyses showed formation of both Mo₂Cnanorods and nanoparticles. The SEM analyses showed a network ofnanorods with nanoparticles distributed within the network as shown inFIG. 1. Accurate dimensions of carbide nanorods have been obtained byHRTEM as shown in FIG. 2, which shows carbide nanorods having diameterssimilar to those of carbon nanotubes, namely, about 7 nm. The carbidenanoparticles particles ranged from about 7 nm to about 25 nm indiameter.

[0223] Sample 12, a stoichiometric mixture, was studied in more detailin order to learn the course of the reaction. The reaction was trackedby thermogravimetric analysis (TGA) as shown in FIG. 4. FIG. 4 showsthat the stoichiometric reaction has occurred in two distinct steps,namely, reduction of MoO₃ by carbon to MoO₂ at from about 450 to about550° C., followed by further reduction to Mo₂C at from about 675° C. toabout 725° C. SEM and XRD analyses taken after calcination at 600° C.showed a complete redistribution of oxide precursor from the very large,supra-micron particles of MoO₃ initially present to about 20 to 50 nmparticles of MoO_(3−x), well-dispersed amongst individual fibrils. Thisredistribution probably occurred through vaporization. Furthercalcination to 800° C. converted the MoO_(3−x) (wherein x is 0 or 1)mixture to Mo₂C nanorods and nanoparticles, with further reduction inparticle size from about 7 to about 25 nm. Without being bound by anytheory, even though redistribution of MoO₃ probably takes place throughvaporization, both chemical transformations (MoO₃→MoO₂ and MoO₂→Mo₂C) byreduction by carbon are believed to occur through solid-solid phasereactions.

[0224] B. Mo₂C Nanoparticles Supported on Carbon Nanotubes

[0225] XRD, SEM and HRTEM analyses of products from Sample 10 providedevidence for the successful preparation of nanoparticles of Mo₂Csupported on individual carbon nanotubes. These products were formed byimpregnation of ammonium molybdate from aqueous solution onto CCaggregates of carbon nanotubes and carefully calcined as shown inTable 1. XRD's of both products showed the cubic form of Mo₂C to be themajor component along with graphitic carbon. Hexagonal Mo₂C was seen asa minor component. No molybdenum oxide was detected. The cubic Mo₂Cparticles ranged from about 2 to about 5 nm in diameter, while thehexagonal particles ranged from about 10 to about 25 nm. The cubicparticles were mainly deposited on individual carbon nanotubes, whilethe hexagonal particles were distributed between carbon nanotubes. Thesecan be seen in FIGS. 3 and 4, which are copies of HRTEM micrographstaken from Sample 10. In these pictures, the particle size can beestimated by direct comparison with the fibril diameters, which rangefrom 7 to 10 mn.

Example 8

[0226] Preparation of Tungsten Carbide Precursors by Impregnation withAmmonium Tungstate

[0227] The procedure used in Example 2 above was followed, except thatthe impregnating solution was an aqueous solution containing the correctamount of ammonium paratungstate hydrate ((NH₄)₁₀W₁₂O₄₁.5H₂O 72% W,referred to as ammonium tungstate) necessary for the desired C:W atomratio loading (C:W mole ratios of 3.5:1, 10:1 and 20:1). The resultingmixture was dried at 225° C. in full vacuum for 18 hours during whichthe paratungstate compound was decomposed to WO₃. The sample was setaside for conversion to carbide catalysts by careful calcination underan inert atmosphere as more particularly described in Example 10.

Example 9

[0228] Preparation of Tungsten Carbide Precursors by Impregnation withPhosphotungstic Acid

[0229] The procedure used in Example 8 above was followed, except thatthe impregnating solution was an aqueous solution containing the correctamount of phosphotungstic acid (H₃ PO₄.12 WO₃.xH₂O, 76.6% W referred toas PTA), necessary for the desired C:W atom ratio loading (C:W moleratios of 3.5:1, 10:1 and 20:1.) The resulting mixture was dried at 225°C. in full vacuum for 18 hours during which the PTA was decomposed toWO₃. The sample was set aside for conversion to carbide catalysts bycareful calcination under an inert atmosphere as more particularlydescribed in Example 10.

Example 10

[0230] Calcination of Tungsten Carbide Precursors at 1000° C.

[0231] The procedure described in Example 7 above was followed toconvert precursors of tungsten carbides to tungsten carbides. Aftercooling in argon, the samples were passivated using 3% O₂/Ar. Table 3below summarizes the experimental conditions and XRD results forselected experiments. TABLE 3 SUMMARY OF RESULTS FOR TUNGSTEN CARBIDEPREPARATIONS SAMPLE W Source T° C. C:W INITIAL PHASES, XRD 1 PTA andCC^(a) 1000 3.5:1  WC and W₂C 2 PTA and CC 1000 10:1 WC and W₂C 3 PTAand CC 1000 20:1 WC and W₂C 4 A. Tung and CC^(b) 1000 3.5:1  WC, W₂C andpossibly W 5 A. Tung and CC 1000 10:1 WC and W₂C 6 A. Tung and CC 100020:1 WC and W₂C

[0232] The chemical reactions involved in the preparation of Samples 1-6summarized in table 3 are:

WO₃(s)+4C→WC+3 CO and 2WO₃(s)+7C→W₂C+6 CO.

[0233] In the second column of Table 3 is a list of tungsten precursorswhich were converted to W₂C/WC by reacting with carbon nanotubes. PTArefers to phosphotungstic acid and A. Tung refers to ammoniumparatungstate hydrate. “(s)” refers to the solid phase of the tungstenprecursor. C:W refers to the ratio of C atoms to W atoms in the originalmix. The stoichiometric atom ratio to produce pure WC with no excess ofC or W is 4.0. To produce pure W₂C, the atom ratio C:W is 3.5. The XRDcolumn lists the compounds observed in the XRD analyses.

Examples 11-13

[0234] Preparation of a Catalyst Support of Extrudates of SiliconCarbide Nanorods

[0235] SiC nanorods were prepared from Hyperion aggregates of carbonnanotubes in accordance with Example 1 of U.S. application Ser. No.08/414,369 filed Mar. 31, 1995 by reacting the carbon nanotubes with ISOvapor at high temperature. The resulting SiC nanorods have a uniformdiameter of fifteen nm on average and a highly crystallized β-SiCstructure.

[0236] Poly(dimethylsiloxane) as provided by Aldrich Chemicals ofMilwaukee, Wis. was used as a binder for the preparation of extrudatesof SiC nanorods. 0.16 g of SiC nanorods and 0.16 g ofpoly(dimethylsiloxane) were mixed to form a uniform thick paste.Subsequently, the paste was pushed through a syringe to produceextrudates having a green color which were heated under flowing argonatmosphere under the following conditions: at 200° C. for 2 hours(Example 11); at 400° C. for 4 hours (Example 12); and at 700° C. for 4hours (Example 13). A rigid porous structure of SiC nanorods was formed.

[0237] The extrudates obtained in Examples 11-13 had a density of 0.97gm/cc and a bimodal pore structure. The macropores were 1 to 5 μm, asshown in FIG. 5B among aggregates and the mesopores were 10 to 50 nm, asshown in FIG. 5C in the networks of intertwined SiC nanorods. Thediameter of the extrudates was about 1.2 nm as shown in FIG. 5A. Thespecific surface area of the extrudates of SiC nanorods was 97 m²/gm.

[0238] Because of their high surface area, unique pore structure andhigh temperature stability, the SiC extrudates are attractive forvarious applications, including as supports for catalysts such asplatinum, palladium other catalytic metals and carbides of Mo, W, V, Nbor Ta. The surface properties of SiC nanorods when used as a catalystsupport are very close to those of carbon. Conventional carbon supportscan therefore be replaced with SiC extrudates. Many properties of carbonsupported catalysts can be realized in high temperature conditions, asrequired, in particular, for oxidation reactions.

Examples 14 and 15

[0239] Preparation by Reductive Carburization of Extrudates of CarbonNanotubes Including Molybdenum Carbides

[0240] Two samples of 5 gms of extrudates of carbon nanotubes having avolatile molybdenum compound on the surface thereof prepared accordingto Example 14 are charged into alumina boats. Each boat is placed into atube furnace and heated under flowing argon for 2 hours at 250° C. and450° C., respectively. The gas is changed from argon to a mixture ofCH₄/H₂ (20% CH₄) and the furnace is slowly (1° C./min) heated up to 650°C. where the temperature is maintained for 1 hour. Molybdenum carbidessupported on the surface of the extrudates of the carbon nanotubes areobtained.

Example 16

[0241] Preparation by Reactive Chemical Transport of Extrudate ofMolybdenum Carbide Nanorods

[0242] One gram of an extrudate of carbon nanotubes, 8 gms of molybdenumpowder and 50 mg of bromine contained in a glass capsule are placed intoa quartz tube which is evacuated at 10⁻³ Torr and then sealed. After thebromine capsule is broken, the tube is placed into a tube furnace andheated at 1000° C. for about 1 week. The extrudates of carbon nanotubesare substantially converted to molybdenum carbide nanorods.

Example 17

[0243] Preparation by Carburization of Molybdenum Carbides Supported onthe Surface of Extrudates of Carbon Nanotubes

[0244] A sample of an extrudate of carbon nanotubes is placed in avertical reactor such that a bed is formed. The extrudate is heatedunder flowing H₂ gas at 150° C. for 2 hours. Thereafter, the extrudateis cooled to 50° C. H₂ gas passed through a saturator containing Mo(CO)₆at 50° C. is passed over the cooled extrudates of carbon nanotubes. As aresult, Mo(CO)₆ becomes adsorbed on the surface of the extrudate.Following the adsorption of Mo(CO)₆, the temperature of the sample israised to 150° C. in an atmosphere of pure H₂. The temperature ismaintained at 150° C. for 1 hour. The temperature of the sample is thenincreased at 650° C. and maintained at this temperature for 2 hoursunder flowing H₂ gas. A sample of the extrudate of carbon havingmolybdenum on its surfaces is obtained. This sample is kept at 650° C.for 1 hour. The gas is switched from H₂ to a CH₄/H₂ mixture (20% CH₄).The molybdenum adsorbed on the surfaces of the carbon nanotubes isconverted to molybdenum carbide. The amount of molybdenum carbide formedon the surface of the extrudate can be controlled, by varying theduration of adsorption of the Mo(CO)₆ over the cooled carbon nanotubeextrudate.

Example 18

[0245] Use of Mo₂C Nanoparticles and/or Nanorods Supported on Aggregatesof Carbon Nanotubes in the Vapor Phase Hydrogenation of Ethylene

[0246] A vapor phase reactor was assembled by inserting a 6 mm quartzthermowell upward through the bottom end of a vertical quartz tubehaving an outer diameter of 12 mm. A porous plug of quartz wool wasplaced at the tip of the thermowell to support a bed of catalyst powder.One gram of the catalyst of Sample No. 2 in Table 1 was crushed andsieved to (+80-60) standard mesh and placed onto the quartz wool plug.The tube was placed vertically into a ½ inch tube furnace as describedin Example 6. The top of the tube was fitted with gas inlet lines tofeed reactant gases, and the bottom of the tube was fitted with an exitline connected to a 0-15 psi pressure gauge. Rotometers in the gas inletlines controlled the flows and thus the ratios of the individualreactant gases. Product gases were fed through a gas sampling valve to aVarian gas chromatograph equipped with a GS-Q capillary column suitablefor analyzing C₁-C₅ alkanes and olefins.

[0247] Ethylene and hydrogen gases were fed to the vapor phase reactordescribed in molar ratios ranging from 1:1 to 4:1 ethylene:H₂ at 70° C.initial temperature, 1-3 psi gauge total pressure at a gas spacevelocity (GSV) 60-325 min⁻¹. In each run, the temperature of thecatalyst bed was held at the set temperature of 70° C. for severalminutes, and then rapidly increased to approximately 200° C. in severalminutes. The temperature of the catalyst bed remained relativelyconstant thereafter. Analyses by gas chromatography showed 100%conversion of ethylene to ethane. Ethane was the only product observed,i.e., the selectivities of the reaction approached 100%.

Example 19

[0248] Preparation of Oxycarbide Containing Nanorods Catalyst In situand Use of in the Vapor Phase Isomerization of Butane to Isobutane

[0249] The catalyst Sample 12 of Table 1 was oxidized to form oxycarbidenanorods. This unsupported catalyst was then used to isomerize butane toisobutane. A 1.0 gram sample of ground catalyst (+80-60) was placed in areactor as described in Example 18. The catalyst was treated with 10% H₂in argon at 700° C. for 30 minutes, cooled in argon to room temperature,and then treated with 3% O₂ in argon at 350° C. for 14 hours to obtainoxycarbide-containing nanorods. After purging the system of O₂, mixturesof n-butane and H₂ in molar ratios of n-butane:H₂ ranging from 1:16 to1:4 at 1-3 psi gauge pressure were fed to the reactor at a WHSV 1 hr⁻¹to 10 hr⁻¹. The products were analyzed by GC using a GS-Q capillarycolumn.

[0250] A steady yield of 4.4% isobutane was obtained at 380° C. at aWHSV 10 hr⁻¹. Conversion of n-butane was approximately 4.5% withselectivity to isobutane of about 96% based on GC analyses. Thebyproducts, in order of abundance, were propane, ethane and methane.Increasing the temperature to 420° C. increased the conversion ofn-butane to more than 10% isobutane. However, the selectivity toisobutane was less than 50%, with the major selectivity loss to methane.

Example 20

[0251] Use of Mo₂C Nanoparticles and/or Nanorods Supported on Extrudatesof Aggregates of Carbon Nanotubes in the Vapor Phase Hydrogenation ofEthylene

[0252] A vapor phase reactor is assembled as described in Example 18.One gram of the catalyst Sample No. 9 in Table 1 is crushed and sievedto (+80-60) standard mesh and placed onto the quartz wool plug. The tubeis placed vertically into a ½ inch tube furnace as described in Example5. The top of the tube is fitted with gas inlet lines to feed reactantgases and the bottom of the tube is fitted with an exit line connectedto a 0-15 psi pressure gauge. Rotometers in the gas inlet lines controlthe flows and thus the ratios of the individual reactant gases. Productgases are fed through a gas sampling valve to a Varian gas chromatographequipped with a GS-Q capillary column.

[0253] Ethylene and hydrogen gases are fed to the vapor phase reactor inmolar ratios ranging from 1:1 to 4:1 ethylene: H₂ at 70° C. initialtemperature, 1-3 psi gauge total pressure at a GSV 60-325 min⁻¹. In eachrun, the temperature of the catalyst bed is held at the set temperatureof 70° C. for several minutes, then rapidly increased to approximately200° C. in several minutes. The temperature of the catalyst bed remainsrelatively constant thereafter. Analyses by GC shows 100% conversion ofethylene to ethane. Ethane is the only product observed, i.e.,selectivities approaching 100%.

Example 21

[0254] Use of Mo₂C Nanoparticles and/or Nanorods Supported on Extrudatesof Aggregates of Carbon Nanotubes in the Vapor Phase Isomerization ofButane to Isobutane

[0255] The catalyst of Sample 11 of Table 1 was oxidized to formoxycarbide nanorods which were used to isomerize butane to isobutane. A1.0 gram sample of ground catalyst (+80-60) was placed in a reactor asdescribed in Example 18. In the reactor, the catalyst was then treatedwith 10% H₂ in argon at 700° C. for 30 minutes, cooled in argon to roomtemperature, and then treated with 3% O₂ in argon at 350° C. for 14hours to obtain oxycarbide nanorods. After purging the system of O₂,mixtures of n-butane and H₂ in molar ratios of n-butane: H₂ ranging from1:16 to 1:4 at 1-3 psi gauge pressure were fed to the reactor at WHSVsranging from 1 to 10 hr⁻¹. The products were analyzed by GC using a GS-Qcapillary column provided by J&W of Alltech Associates.

[0256] A steady yield of 4.4% isobutane was obtained at 380° C. at aWHSV 10 hr⁻¹. Conversion of n-butane was approximately 4.5% withselectivity to isobutane of about 96% based on GC analyses. Thebyproducts, in order of abundance, were propane, ethane and methane.Increasing temperature to 420° C. increased conversion of n-butane tomore than 10%. The selectivity to isobutane was less than 50%, with themajor selectivity loss to methane.

Example 22

[0257] Use of Mo₂C Nanoparticles and/or Nanorods Supported on Aggregatesof Carbon Nanotubes in the Hydrodesulfurization of Thiophene

[0258] 0.1 gm of the catalyst of Sample 2 in Table 1 is charged into a500 cc stirred autoclave with 300 cc of 1 vol % solution of thiophene inhexadecane. The reactor is charged to 80 atm with H₂ and thehydrodesulfurization reaction is carried out at 300° C. One cc samplesare withdrawn and analyzed at 5-minute intervals and a pseudo firstorder rate constant for disappearance of thiophene is determined to be4.5×10⁻³ L/gm cat-s.

Example 23

[0259] Use of Unsupported Oxycarbide Nanorods as Catalyst in theHydrodesulfurization of Thiophene

[0260] 0.1 gm of catalyst described in Example 19 above is charged intoa 500 cc stirred autoclave with 300 cc of 1 vol % solution of thiophenein hexadecane. The reactor is charged to 80 atm with H₂ and thehydrodesulfurization reaction is carried out at 300° C. One cc samplesare withdrawn and analyzed at 5 minute intervals and a pseudo firstorder rate constant for disappearance of thiophene is determined to be4.5×10⁻³ L/gm cat-s.

Example 24

[0261] Use of WC/W₂C Nanoparticles and/or Nanorods Supported onAggregates of Carbon Nanotubes in the Vapor Phase Hydrogenation ofEthylene

[0262] A vapor phase reactor is assembled as described in Example 18.One gram of the catalyst of Sample 1 in Table 3 is crushed and sieved to(+80-60) standard mesh and placed onto the quartz wool plug. The tube isplaced vertically into a ½ inch tube furnace as described in Example 10.The top of the tube is fitted with gas inlet lines to feed reactantgases, and the bottom of the tube is fitted with an exit line connectedto a 0-15 psi pressure gauge. Rotometers in the gas inlet lines controlthe flows and thus the ratios of the individual reactant gases. Productgases are fed through a gas sampling valve to a Varian gas chromatographequipped with a GS-Q capillary column suitable for analyzing C₁-C₅alkanes and olefins.

[0263] Ethylene and hydrogen gases are fed to the vapor phase reactor inmolar ratios ranging from 1:1 to 4:1 ethylene: H₂ at 70° C. initialtemperature, 1-3 psi gauge total pressure and at WHSVs of 65-325 min⁻¹.In each run, the temperature of the catalyst bed is held at the settemperature of 70° C. for several minutes, then it is rapidly increasedto approximately 200° C. in several minutes. The temperature of thecatalyst bed remains relatively constant thereafter. Analyses by GCshows 100% conversion of ethylene to ethane. Ethane is the only productobserved, i.e., the selectivities approach 100%.

Example 25

[0264] Preparation of Tungsten Oxycarbide Nanorods Catalyst In Situ andUse of Same in the Vapor Phase Isomerization of Butane to Isobutane

[0265] The catalyst of Sample 2 of Table 3 is oxidized to formunsupported oxycarbide nanorods which are used to isomerize butane toisobutane. A 1-gram sample of ground catalyst (+80-60) is placed in areactor as described in Example 24. In the reactor, the catalyst istreated with 10% H₂ in argon at 700° C. for 30 minutes, cooled in argonto room temperature, and then treated with 3% O₂ in argon at 350° C. for14 hours to obtain tungsten oxycarbide containing nanorods. Afterpurging the system of O₂, mixtures of n-butane and H₂ in molar ratios ofn-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gauge pressure are fedto the reactor at WHSVs of 1 to 10 hr⁻¹. The products are analyzed by GCusing a GS-Q capillary column as provided by Alltech Associates.

[0266] A steady yield of 4.4% isobutane is obtained at 380° C. and at aWHSV of 1 to 10 hr⁻¹. Conversion of n-butane is approximately 4.5% withselectivity to isobutane of about 96% based on GC analyses. Thebyproducts, in order of abundance, are propane, ethane and methane.Increasing temperature to 420° C. increases conversion of n-butane tomore than 10% isobutane. The selectivity to isobutane is less than 50%with the major selectivity loss to methane.

Example 26

[0267] Use of WC/W₂C Nanoparticles and/or Nanorods Supported onAggregates of Carbon Nanotubes in the Hydrodesulfurization of Thiophene

[0268] 0.1 gram of the catalyst of Sample 1 in Table 3 is charged into a500 cc stirred autoclave with 300 cc of 1 vol % solution of thiophene inhexadecane. The reactor is charged to 80 atm with H₂ and thehydrodesulfurization reaction is carried out at 300° C. One cc samplesare withdrawn and analyzed at 5-minute intervals and a pseudo firstorder rate constant for disappearance of thiophene is determined to be4.5×10⁻³ L/gm cat-s.

Example 27

[0269] Use of Unsupported Tungsten Oxycarbide Nanorods as Catalyst inthe Hydrodesulfurization of Thiophene

[0270] 0.1 gram of the catalyst in Example 25 is charged into a 500 ccstirred autoclave with 300 cc of 1 vol % solution of thiophene inhexadecane. The reactor is charged to 80 atm with H₂, and thehydrodesulfurization reaction is carried out at 300° C. One cc samplesare withdrawn and analyzed at 5-minute intervals and a pseudo firstorder rate constant for disappearance of thiophene is determined to be4.5×10⁻³ L/gm cat-s.

Example 28

[0271] Preparation of a Pd Catalyst Supported on SiC Extrudates

[0272] A 5 weight % Pd/SiC extrudate catalyst is prepared by contacting10.0 gm SiC extrudates prepared in Example 12 with a solution containing1.455 gms Pd(acetylacetonate)₂ (34.7% Pd, obtained from Alfa/Aesar ofWard Hill, Mass.) dissolved in 500 cc toluene. The mixture is stirredlightly for 1 hour, after which the toluene is removed at reducedpressure and 40° C. in a rotary evaporator. The resulting dark brownsolids are dried at 80° C. overnight, then calcined at 350° C. in airfor 16 hours.

Example 29

[0273] Preparation of a Pt Catalyst Supported on SiC Extrudates

[0274] A 1 weight % Pt/SiC extrudate catalyst is prepared by contacting10.0 gms SiC extrudates prepared in Example 12 with a 6 N HCl solutioncontaining 0.174 gram PtCl₄ (58% Pt, obtained from Alfa/Aesar). Themixture is stirred lightly for 1 hour after which solvent is removed atreduced pressure and 70° C. in a rotary evaporator. The resulting brownsolids are dried at 140° C.

Example 30

[0275] Oxidation of CH₄ with the Pd/SiC Extrudate Catalyst Prepared inExample 28

[0276] Five gms of catalyst prepared in Example 28 are packed into avertical b {fraction (1/2)}″ stainless steel tubular reactor to a heightof about 2½″. A wad of quartz wool placed atop a ¼″ stainless steelthermowell inserted upward from the bottom of the tube supports thecatalyst bed. The inlet and outlet of the tube reactor are fitted toallow passage of gas into the reactor, through the catalyst bed and outof the reactor. The effluent gas is analyzed by a gas chromatographusing a Poropak Q column manufactured by Millipore Corp. of Bedford,Mass., which allows quantitative analysis of CH₄, CO and CO₂.Temperature of the reactor is measured by a thermocouple inserted in thethermowell. The reactor is then placed in a 1″ Lindberg furnace toprovide heat.

[0277] The catalyst is reduced in situ with 5% H₂/N2 at 350° C. for 12hours. After purging residual H₂ with N₂, at atmospheric pressure, a gasmixture comprising 4% O₂/1% CH₄/95% N₂ is passed over the catalyst bedat 450° C. at a total gas rate of 50 l (stp)/hr. Gas chromatographanalysis shows a conversion of CH₄>99 mole % at about 100% selectivityto CO₂.

Example 31

[0278] Oxidation of CO with the Pt/SiC Extrudate Catalyst Prepared inExample 29

[0279] The reactor used in Example 30 is loaded with 5 gms of catalyst.The catalyst is reduced in situ with 5% H₂/N₂ for 2 hours at 350° C.,after which the reactor is purged of H₂ by N₂. At atmospheric pressure,a gas mixture comprising 5% O₂/1% CO and 94% argon is passed over thecatalyst at 300° C. at a total gas rate of 40 1 (stp)/hr. Gaschromatographic analyses show complete conversion of CO to CO₂.

EXAMPLES OF MAKING ACIDIFIED CARBIDES AND/OR OXYCARBIDES Example 32

[0280] Halogen Treatment of Oxygenated Molybdenum Carbide

[0281] Two gms samples from Examples 5, 6 or 7 are placed in a 1-inchmicro-reactor. First the reactor temperature is raised to 600° C. underflow of argon to dry the sample. The carrier gas is then switched to 5%Cl₂/Ar and the chlorination is allowed to proceed at 300° C. for 1 hour.Upon completion, the sample is cooled down and purged with argon for 30minutes and stored under argon.

Example 33

[0282] Carbon Tetrachloride Treatment of Oxygenated Molybdenum Carbide

[0283] Two gms samples from Examples 5, 6 or 7 are placed in a 1-inchmicro-reactor. First the reactor temperature is raised to 600° C. underflow of argon to dry the sample. The carrier gas is then passed througha gas-liquid saturator containing pure CCl₄. The temperature of thesaturator is kept at 0° C. in an ice-water bath. Chlorination is allowedto proceed at 300° C. for 1 hour. Upon completion, the sample is cooleddown and purged with argon for 30 minutes and stored under argon.

Example 34

[0284] Halogen Treatment of Hydrogen Pretreated Molybdenum Carbide

[0285] Two gms samples prepared using the procedure described inExamples 5, 6 or 7 are placed in a 1-inch micro-reactor and heated inhydrogen at temperatures up to 500° C. After 30 minutes of treatment,the reactor is cooled to 200° C. and purged with argon. The carrier gasis then switched to 5% C1 ₂/Ar and the chlorination is allowed toproceed at 200° C. for 2 hours. Upon completion, the sample is cooleddown and purged with argon for 30 minutes and stored under argon.

Example 35

[0286] Carbon Tetrachloride Treatment of Hydrogen Pretreated MolybdenumCarbide

[0287] Two gms samples prepared using the procedure described inExamples 5, 6 or 7 are placed in a 1-inch micro-reactor and heated inhydrogen at temperatures up to 500° C. After 30 minutes of treatment,the reactor is cooled to 200° C. and purged with argon. The carrier gasis then passed through a gas-liquid saturator containing pure CCl₄. Thetemperature of the saturator is kept at 0° C. in an ice-water bath.Chlorination is allowed to proceed at 200° C. for 2 hours. Uponcompletion, the sample is cooled down and purged with argon for 30minutes and stored under argon.

Example 36

[0288] Acidifying Mo Carbide Surface with Ammonia

[0289] Two gms samples prepared using the procedure described inExamples 5, 6 or 7 were placed in a 1-inch micro-reactor. Theacidification was carried out by reacting the samples with NH₃ attemperatures up to 700° C. After the reaction, the samples were held at700° C. for 1 hour, the reactor was then purged with N₂ and cooled downto room temperature. The treated sample was then stored under N₂.

Example 37

[0290] Acidifying Mo Carbide Surface with Phosphate

[0291] Ammonium phosphate ((NH₄)H₂PO₄) was added to nanotubes byincipient wetness impregnation. The loading was typically in the rangeof 0.2-5 mol %. The impregnated sample was then dried and calcined inair at 300° C. for 2 hours. The modified fibrils were designated as PF.

[0292] A procedure similar to that used in Example 2 above followedexcept the powdery samples of CC aggregates were replaced by PF. Thecalcined samples having the desired C:Mo ratio were set aside forconversion to carbide catalysts by careful calcination under an inertatmosphere as described in Examples 6 or 7. Post-synthesis XPS analysisindicated that phosphorus was strongly bonded to Mo atoms.

Example 38

[0293] Incorporation of AlCl₃ onto Molybdenum CarbideNanorods/Nanoparticles

[0294] Molybdenum carbide nanorods or nanoparticles are preparedfollowing the procedures described in Examples 1-7. The C:Mo atomicratio is controlled at 5 or lower to obtain a pure or highlyconcentrated molybdenum carbide phase. Both XRD and SEM confirm theformation of β-Mo₂C -containing nanorods or nanoparticles. The preparedsamples are transferred into a three-neck flask under an argon blanket.An ethanol solution of AlCl₃ is then added using the incipient wetnessmethod amount. The resulting mixture is dried at 110° C. under argon andthen calcined at 200° C. for 1 hour.

Example 39

[0295] Incorporation of Chlorinated Alumina on Mo Carbide ContainingAggregates by Co-Impregnation of Al(NO₃)₃. 9H₂O and (NH₄)6Mo7O24Followed by Chlorination

[0296] As grown CC or CY nanotube aggregates were oxidized with nitricacid as described in Example 3 to form oxidized CC aggregates having anacid titer of about 0.6 meq/gm.

[0297] Five gms oxidized CC aggregates are impregnated by incipientwetness with aqueous solutions containing the amount of ammoniumheptamolybdate tetrahydrate and aluminum nitrate necessary for thedesired C:Mo:Al atomic ratio. The resulting mixtures are dried at 225°C. in full vacuum for 18 hours during which time the heptamolybdate andthe aluminum nitrate are decomposed to MoO₃ and Al₂O₃.

[0298] Weighed samples of molybdenum carbide-alumina precursors areloaded into porcelain boats that were then placed horizontally in a1-inch quartz tube. The procedure described in Example 7 is followed attemperatures up to 1000° C. XRD phase analysis indicates that the finalform of Mo and Al compounds are β-Mo₂C and Al₂O₃. After cooling down toroom temperature under argon, the carrier gas is passed through agas-liquid saturator containing pure CCl₄. The temperature of thesaturator is kept at 0° C. in an ice-water bath. Chlorination is allowedto proceed at 200° C. for 2 hours. Upon completion, the sample is cooleddown and purged with argon for 30 minutes and stored under argon.

Example 40

[0299] Incorporation of Zirconia in Molybdenum Carbide Catalyst

[0300] As grown CC or CY nanotube aggregates were oxidized with nitricacid as described in Example 3 to form oxidized CC aggregates having anacid titer of about 0.6 meq/gm.

[0301] Five gms oxidized CC type aggregates are impregnated by incipientwetness with aqueous solutions containing the amount of ammoniumheptamolybdate tetrahydrate and zirconium dinitrate oxide(ZrO(NO₃)₂.xH₂O) necessary for the desired C:Mo:Zr atomic ratio. Theresulting mixtures are dried at 225° C. in full vacuum for 18 hoursduring which the heptamolybdate and the aluminum nitrate are decomposedto MoO₃ and ZrO₂.

[0302] The solids are then placed horizontally in a 1-inch quartz tube.The procedure in Example 5 is followed at temperatures up to 900° C.

EXAMPLES SHOWING REACTIONS CONDUCTED USING THE CATALYSTS OF THEINVENTION Example 41

[0303] Preparation of Oxycarbide Nanorods Catalyst In Situ and Use ofSame in the Vapor Phase Isomerization of n-Butane to Isobutane

[0304] A molybdenum carbide nanorod catalyst was prepared using theprocedure described in Example 2 with C:Mo=3.5 followed by a calcinationprocedure described in Example 6. This catalyst was oxidized to formunsupported oxycarbide nanorods which were used to isomerize n-butane toisobutane.

[0305] A vapor phase reactor as described in Example 18 was assembled.One gram of ground catalyst, approximately 60 to 80 mesh, was placedonto the quartz wool plug. In the reactor, the catalyst was treated with10% hydrogen in argon at 700° C. for 30 minutes, cooled in argon to roomtemperature, and then treated with 3% oxygen in argon at 350° C. for 14hours to obtain oxycarbide nanorods. After purging the system of oxygen,mixtures of n-butane and hydrogen in molar ratios of n-butane:H₂ rangingfrom 1:16 to 1:4 at 1-3 psi gauge pressure were fed to the reactor atWHSVs of 1-10 h⁻¹. A steady yield of 4.4% isobutane was obtained at 380°C. at a WHSV of 10 h⁻¹. Conversion of n-butane was approximately 4.5%with selectivity to isobutane of about 96% based on GC analyses. Thebyproducts, in order of abundance, were propane, ethane and methane.Increasing the temperature to 420° C. increased conversion of n-butaneto more than 10% at selectivities to isobutane less than 50%. The majorselectivity loss to methane.

Example 42

[0306] n-Butane Isomerization with Chlorine-treated Molybdenum CarbideCatalyst

[0307] One gram of the catalyst in Example 32 is placed in themicro-reactor described above in Example 18. Mixtures of n-butane and H₂in molar ratios of n-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gaugepressure are passed through a liquid saturator containing pure CCl₄ heldat −20° C. and fed to the reactor at WHSVs of 1-10 h⁻¹. At 300° C., asteady butane conversion of about 20% is achieved with selectivity toisobutane of more than 96%.

Example 43

[0308] n-Butane Isomerization with AlCl₃/Molybdenum Carbide Catalyst

[0309] One gram of the catalyst of Example 38 is placed in themicro-reactor described in Example 18. Mixtures of n-butane and H₂ inmolar ratios of n-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gaugepressure are passed through a liquid saturator containing pure CCl₄ heldat −20° C. and fed to the reactor at WHSVs of 1-10 h⁻¹. At 300° C., asteady butane conversion of about 50% is achieved with selectivity toisobutane of more than 96%.

Example 44

[0310] n-Butane Isomerization with Chlorinated MolybdenumCarbide-Alumina Catalyst

[0311] One gram of the catalyst of Example 14 is placed in themicro-reactor described in Example 18. Mixtures of n-butane and H₂ inmolar ratios of n-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gaugepressure are passed through a liquid saturator containing pure CCl₄ heldat −20° C. and fed to the reactor at WHSVs of 1-10 h⁻¹. At 300° C., asteady butane conversion of about 50% is achieved with selectivity toisobutane of more than 96%.

Example 45

[0312] n-Butane Isomerization with Treated with Ammonia MolybdenumCarbide Catalyst

[0313] One gram of the catalyst of Example 36 is placed in themicro-reactor described in Example 18. Mixtures of n-butane and H₂ inmolar ratios of n-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gaugepressure are fed to the reactor at WHSVs of 1-10 h⁻¹. At 300° C., asteady butane conversion of about 10% is achieved with selectivity toisobutane of more than 96%.

Example 46

[0314] n-Butane Isomerization with Phosphorus-Incorporated MolybdenumCarbide Catalyst

[0315] One gram the catalyst of Example 37 is placed in themicro-reactor in Example 18. Mixtures of n-butane and H₂ in molar ratiosof n-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gauge pressure arefed to the reactor at WHSVs of 1-10 h⁻¹. At 300° C., a steady butaneconversion of about 10% is achieved with selectivity to isobutane ofmore than 96%.

Example 47

[0316] n-Butane Isomerization with Molybdated Zirconia/MolybdenumCarbide Catalyst

[0317] One gram of the catalyst made from Example 40 is placed in themicro-reactor described in Example 18. The catalyst is first treatedwith 3% O₂ in argon at 350° C. for 12 hours to obtain molybdatedzirconia. After purging the system of O₂, mixtures of n-butane and H₂ inmolar ratios of n-butane:H₂ ranging from 1:16 to 1:4 at 1-3 psi gaugepressure are fed to the reactor at WHSVs of 1-10 h⁻¹. At 350° C., asteady butane conversion of about 10% is achieved with selectivity toisobutane of more than 96%. TABLE 4 SUMMARY OF RESULTS FOR ISOMERIZATIONOF n-BUTANE TO ISOBUTANE ISO- n-BUTANE BUTANE CONVER- SELEC- SAMPLECATALYST T° C. SION TIVITY 41 Unsupported Oxycarbide 380  4.5%   96%Nanorods 41 Unsupported Oxycarbide 420 10% <50% Nanorods 42 Cl TreatedMo₂C 300 20% >96% 43 AlCl₃/Mo₂C 300 50% >96% 44 Cl Mo₂C-Alumina 30050% >96% 45 Treated with Ammonia 300 10% >96% Mo₂C 46 P Incorporated 30010% >96% Mo₂C 47 Molybdated Zirconia/ 350 10% >96% Mo₂C

[0318] As shown in Table 4, the untreated catalysts achieve conversionsbetween 4.5% and 10% and selectivities to isobutane of from <50% to 96%.In contrast, the acidified catalytic compositions achieve conversionsgreater than 10% and selectivities to isobutane of greater than 96%. Thereactions using the acidified catalytic compositions are also run atlower temperatures than reactions using untreated catalysts.

Example 48

[0319] 1-Butene Isomerization with Chlorinated MolybdenumCarbide-Alumina Catalyst

[0320] One gram the catalyst of Example 14 is placed in themicro-reactor as described in Example 18. Mixtures of 1-butene and H₂ inmolar ratios of 1-butene:H₂ ranging from 1:16 to 1:4 at 1-3 psi gaugepressure are fed to the reactor at WHSVs of 1-10 h⁻¹. At 80° C., asteady 1-butene conversion of about 30% is achieved with selectivity to2-butene of more than 96%.

[0321] The terms and expressions which have been employed are used asterms of description and not of limitations, and there is no intentionin the use of such terms or expressions of excluding any equivalents ofthe features shown and described as portions thereof, it beingrecognized that various modifications are possible within the scope ofthe invention.

[0322] Thus, while there had been described what are presently believedto be the preferred embodiments of the present invention, those skilledin the art will appreciate that other and further modifications can bemade without departing from the true scope of the invention, and it isintended to include all such modifications and changes as come withinthe scope of the claims.

What is claimed:
 1. A catalytic composition comprising: a plurality ofnanostructures selected from the group consisting of carbon nanotubes,carbide nanorods, and mixtures thereof, each having a substantiallyuniform diameter between 1 nm and 100 nm and a length to diameter ratiogreater than 5, said nanostructures further including a metal carbideselected from the group consisting of carbides and oxycarbides of atransition metal, rare earth metal or actinide, said composition havingan ammonia desorption peak at a temperature greater than 100° C.
 2. Thecatalytic composition of claim 1, wherein said metal is selected fromthe group consisting of titanium, tantalum, niobium, zirconium, hafnium,molybdenum, vanadium and tungsten.
 3. The catalytic composition of claim1, wherein said nanostructures are substantially cylindrical, havegraphitic layers concentric with their cylindrical axes and aresubstantially free of pyrolytically deposited carbon.
 4. The catalyticcomposition of claim 1, wherein said composition includes 10% to 95%carbides by weight thereof.
 5. The catalytic composition of claim 4,wherein said composition includes 0.5% to 25% oxycarbides by weight oftotal carbides.
 6. The catalytic composition of claim 1, wherein saidcatalytic composition is bifunctional.
 7. A catalytic compositioncomprising: a plurality of nanostructures selected from the groupconsisting of carbon nanotubes, carbide nanorods, and mixtures thereof,each having a substantially uniform diameter between 1 nm and 100 nm anda length to diameter ratio greater than 5, said nanostructures furtherincluding a metal carbide selected from the group consisting of carbidesand oxycarbides of a transition metal, rare earth metal or actinide,said nanostructures having been modified by an acidification treatment.8. The catalytic composition of claim 7, wherein said metal is selectedfrom the group consisting of titanium, tantalum, niobium, zirconium,hafnium, molybdenum, vanadium and tungsten.
 9. The catalytic compositionof claim 7, wherein said acidification treatment is treatment with anacidifying compound.
 10. The catalytic composition of claim 9, whereinsaid acidifying compound includes an element selected from the groupconsisting of bromine, chlorine, fluorine, iodine, nitrogen, phosphorus,oxygen, sulfur and any combination thereof.
 11. The catalyticcomposition of claim 10, wherein said acidification treatment isselected from the group consisting of halogenation, chlorination,nitrogenation, oxygenation, and phosphorylation.
 12. The catalyticcomposition of claim 7, wherein said nanostructures are substantiallycylindrical, have graphitic layers concentric with their cylindricalaxes and are substantially free of pyrolytically deposited carbon. 13.The catalytic composition of claim 7, wherein said composition includes10% to 95% carbides by weight thereof.
 14. The catalytic composition ofclaim 13, wherein said composition further includes 0.5% to 25%oxycarbides by weight total carbides.
 15. The catalytic composition ofclaim 7, wherein said catalytic composition is bifunctional.
 16. Acatalytic composition comprising: (a) a rigid porous structure formedfrom a plurality of nanostructures selected from the group consisting ofcarbon nanotubes, carbide nanorods, and mixtures thereof, each having asubstantially uniform diameter between 1 nm and 100 nm and a length todiameter ratio greater than 5, said nanostructures further including ametal carbide selected from the group consisting of carbides andoxycarbides of a transition metal, rare earth metal or actinide, saidrigid porous structure including a plurality of interstitial spacesbetween said nanostructures; and (b) a solid acid in said interstitialspaces.
 17. The catalytic composition of claim 16, wherein said metal isselected from the group consisting of titanium, tantalum, niobium,zirconium, hafnium, molybdenum, vanadium and tungsten.
 18. The catalyticcomposition of claim 16, wherein said nanostructures are substantiallycylindrical, have graphitic layers concentric with their cylindricalaxes and are substantially free of pyrolytically deposited carbon. 19.The catalytic composition of claim 16, wherein said solid acid is acompound containing an element selected from the group consisting ofaluminum and zirconium.
 20. The catalytic composition of claim 19,wherein said solid acid is a compound containing aluminum and the solidacid has been chlorinated, sulfated, or phosphated.
 21. The catalyticcomposition of claim 19, wherein said solid acid is a compoundcontaining zirconium and the solid acid has been chlorinated, sulfated,or phosphated.
 22. The catalytic composition of claim 16, wherein saidrigid porous structure has a density greater than about 0.5 gm/cm³ and aporosity greater than about 0.8 cc/gm.
 23. The catalytic composition ofclaim 22, wherein said rigid porous structure is substantially free ofmicropores and has a crush strength greater than about 1 lb/in².
 24. Thecatalytic composition of claim 16, wherein said composition includes 10%to 95% carbides by weight thereof.
 25. The catalytic composition ofclaim 24, wherein said composition includes 0.5% to 25% oxycarbides byweight total carbides.
 26. The catalytic composition of claim 16,wherein said composition is bifunctional.
 27. A process of preparing acatalytic composition for conducting a fluid phase catalytic reactioncomprising the step of: acidifying a plurality of nanostructuresselected from the group consisting of carbon nanotubes, carbidenanorods, and mixtures thereof, each having a substantially uniformdiameter between 1 nm and 100 nm and a length to diameter ratio greaterthan 5, said nanostructures further including a metal carbide selectedfrom the group consisting of carbides and oxycarbides of a transitionmetal, rare earth metal or actinide.
 28. The process of claim 27,wherein acidifying said nanostructures comprises using an acidifyingcompound containing an element selected from the group consisting ofbromine, chlorine, fluorine, iodine, nitrogen, phosphorus, sulfur,oxygen and mixtures thereof.
 29. The process of claim 28, whereinacidifying said nanostructures further comprises placing saidnanostructures in a reactor; and drying said nanostructures.
 30. Theprocess of claim 29, wherein acidifying said nanostructures farthercomprises passivating the plurality of nanostructures with oxygen. 31.The process of claim 27, wherein acidifying said nanostructures isachieved by chlorination, nitration, sulfation, or phosphorylation. 32.A process of preparing a catalytic composition for conducting a fluidphase catalytic reaction comprising the step of: incorporating a solidacid within the plurality of interstitial spaces within a compositionincluding a plurality of nanostructures selected from the groupconsisting of carbon nanotubes, carbide nanorods, and mixtures thereof,each having a substantially uniform diameter between 1 nm and 100 nm anda length to diameter ratio greater than 5, said nanostructures furtherincluding a metal carbide selected from the group consisting of carbidesand oxycarbides of a transition metal, rare earth metal or actinide. 33.The process of claim 32, further comprising passivating said compositionwith oxygen.
 34. The process of claim 32, wherein said solid acid is acompound containing an element selected from the group consisting ofaluminum and zirconium.
 35. The process of claim 34, wherein said solidacid is a compound containing aluminum and said solid acid has beenchlorinated, sulfated, or phosphated.
 36. The process of claim 34,wherein said solid acid is a compound containing zirconium and saidsolid acid has been chlorinated, sulfated, or phosphated.
 37. A methodfor the isomerization of a hydrocarbon comprising the step of:contacting a feed stream including a hydrocarbon under isomerizationconditions with a composition, said composition including a plurality ofnanostructures selected from the group consisting of carbon nanotubes,carbide nanorods, and mixtures thereof, each having a substantiallyuniform diameter between 1 nm and 100 nm and a length to diameter ratiogreater than 5, said nanostructures further including a metal carbideselected from the group consisting of carbides and oxycarbides of atransition metal, rare earth metal or actinide, said composition havingan ammonia desorption peak at a temperature greater than 100° C.
 38. Themethod of claim 37, wherein said hydrocarbon is selected from the groupconsisting of normal, branched, and cyclic hydrocarbons.
 39. The methodof claim 37, wherein said hydrocarbon is an alkene.
 40. The method ofclaim 37, wherein said isomerization conditions include a temperaturefrom 100° C. to 400° C., a molar ratio of hydrocarbon to hydrogen of1:16 to 1:4, a pressure from about 1 to 10 psi, and a WHSV from 1 to 10h⁻¹.
 41. A method for the isomerization of a hydrocarbon comprising thestep of: contacting a feed stream including a hydrocarbon underisomerization conditions with a composition, said composition includinga plurality of nanostructures selected from the group consisting ofcarbon nanotubes, carbide nanorods, and mixtures thereof, each having asubstantially uniform diameter between 1 nm and 100 nm and a length todiameter ratio greater than 5, said nanostructures further including ametal carbide selected from the group consisting of carbides andoxycarbides of a transition metal, rare earth metal or actinide, saidnanotubes having been modified by an acidification treatment.
 42. Themethod of claim 41, wherein said hydrocarbon is selected from the groupconsisting of normal, branched, and cyclic hydrocarbons.
 43. The methodof claim 41, wherein said hydrocarbon is an alkene.
 44. The method ofclaim 41, wherein said isomerization conditions include a temperaturefrom 100° C. to 400° C., a molar ratio of hydrocarbon to hydrogen of1:16 to 1:4, a pressure from about 1 to 10 psi, and a WHSV from 1 to 10h⁻¹.
 45. The method of claim 41, wherein said acidification treatment istreatment with an acidifying compound.
 46. The method of claim 45,wherein said acidification treatment is selected from the groupconsisting of halogenation, chlorination, nitrogenation, oxygenation,and phosphorylation.
 47. A method for the isomerization of a hydrocarboncomprising the step of: contacting a feed stream including a hydrocarbonunder isomerization conditions with a composition, said compositionincluding: (a) a rigid porous structure formed from a plurality ofnanostructures selected from the group consisting of carbon nanotubes,carbide nanorods, and mixtures thereof, each having a substantiallyuniform diameter between 1 nm and 100 nm and a length to diameter ratiogreater than 5, said nanostructures further including a metal carbideselected from the group consisting of carbides and oxycarbides of atransition metal, rare earth metal or actinide, said rigid porousstructure including a plurality of interstitial spaces between saidnanostructures; and (b) a solid acid in said interstitial spaces. 48.The method of claim 47, wherein said hydrocarbon is selected from thegroup consisting of normal, branched, and cyclic hydrocarbons.
 49. Themethod of claim 47, wherein said hydrocarbon is an alkene.
 50. Themethod of claim 47, wherein said isomerization conditions include atemperature from 100° C. to 400° C., a molar ratio of hydrocarbon tohydrogen of 1:16 to 1:4, a pressure from about 1 to 10 psi, and a WHSVfrom 1 to 10 h⁻¹.
 51. The method of claim 47, wherein said solid acid isa compound containing an element selected from the group consisting ofaluminum and zirconium.
 52. The method of claim 51, wherein said solidacid is a compound containing aluminum and the solid acid has beenchlorinated, sulfated, or phosphated.
 53. The method of claim 51,wherein said solid acid is a compound containing zirconium and the solidacid has been chlorinated, sulfated, or phosphated.
 54. The method ofclaim 47, wherein said rigid porous structure has a density greater thanabout 0.5 gm/cm³ and a porosity greater than about 0.8 cc/gm.
 55. Themethod of claim 54, wherein said rigid porous structure is substantiallyfree of micropores and has a crush strength greater than about 1 lb/in².